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Sample records for earth element ce

  1. Competition Between Organic Matter and Solid Surface for Cation Sorption: Ce and Rare Earth Element as Proxy

    NASA Astrophysics Data System (ADS)

    Davranche, M.; Pourret, O.; Gruau, G.; Dia, A.

    2006-12-01

    Aquatic or soil organic matter are well-known to be strong adsorbent of many cations due to their adsorption capacity. Among these cations, the trivalent rare earth element (REE) and particularly Ce seem to be promising tools to investigate the impact of competition in between organic or inorganic ligands. Ce (III) is oxidized into Ce (IV) by oxidative surface such as Fe and Mn oxyhydroxides. Since Ce (IV) is preferentially adsorbed (as compared to other REE), a positive and negative Ce anomaly is developed respectively onto the solid and within the solution. Previous studies (Davranche et al., 2004, 2005) highlighted the suppression of this feature when Ce occurs to be complexed with organic matter (as humate species). Recent experiments were designed to evaluate the competition between humate and Mn oxide for REE complexation (each reactant being added simultaneously). Two parameters control the competition: time and pH. While organic matter does adsorb immediately the free REE, a desorption of REE occurs through time. Desorption is marked by the development of a Ce anomaly in the REE pattern that reflects the complexation with Mn oxide surface. Along the time, solid surface becomes thus more competitive than the organic matter. PH still influences the competition since at basic pH, REE and organic matter - probably as REE-organic complexes - are adsorbed onto the solid surface. Ultrafiltration analyses at 5 KD were also performed to separate organic matter and organic complexes from the solution. Results provide evidence that in presence of a solid surface, HREE (high rare earth element) desorption from the organic matter occurs through time. This leads to HREE enrichment in solution. All these results suggest that complexation of organic matter is kinetically favoured as compared to the complexation with solid surfaces. However, the organic complex formed during the first stage of the complexation process involves weak bindings. These bindings are easily broken

  2. Rare earth elements in Japan Sea sediments and diagenetic behavior of Ce/Ce∗: Results from ODP Leg 127

    NASA Astrophysics Data System (ADS)

    Murray, Richard W.; Buchholtzten Brink, Marilyn R.; Brumsack, Hans J.; Gerlach, David C.; Russ, G. Price

    1991-09-01

    The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the recorded rare earth element (REE) chemistry of Japan Sea sediments are evaluated by investigating REE total abundances and relative fractionations in 59 samples from Ocean Drilling Program Leg 127. REE total abundances (ΣREE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 (Yamato Basin) overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the late Miocene-Pliocene diatomaceous sequence. Eu/Eu∗ values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu∗ with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. ΣREE at Site 795 (Japan Basin) also is affiliated strongly with aluminosilicate phases, yet is diluted only slightly by siliceous input. At Site 797 (Yamato Basin), REE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. The biogenic influence is largest at Site 794, moderately developed at Site 797, and of only minor importance at Site 795, reflecting basinal contrasts in productivity such that the Yamato Basin records greater biogenic input than the Japan Basin, while the most productive waters overlie the easternmost sequence of Site 794. Ce/Ce∗ profiles at all three sites increase monotonically with depth, and record progressive diagenetic LREE fractionation. The observed Ce/Ce∗ record does not respond to changes in oxygenation state of the overlying water, and Ce/Ce∗ correlates slightly better with depth than with age. The downhole increase in Ce

  3. Role of vacancies, light elements and rare-earth metals doping in CeO2.

    PubMed

    Shi, H; Hussain, T; Ahuja, R; Kang, T W; Luo, W

    2016-01-01

    The magnetic properties and electronic structures of pure, doped and defective cerium oxide (CeO2) have been studied theoretically by means of ab initio calculations based on the density function theory (DFT) with the hybrid HF/DFT technique named PBE0. Carbon (C), nitrogen (N), phosphorus (P), sulphur (S), lanthanum (La) and praseodymium (Pr) doped in CeO2 and CeO2 containing oxygen vacancies (Ov) were considered. Our spin-polarized calculations show that C, N, Pr dopants and Ov defects magnetize the non-magnetic CeO2 in different degree. The optical band gap related to photocatalysis for pure CeO2, corresponding to the ultraviolet region, is reduced obviously by C, N, S, Pr impurities and oxygen vacancies, shifting to the visible region and even further to the infrared range. Especially, N-, S- and Pr-doped CeO2 could be used to photocatalytic water splitting for hydrogen production. As the concentration of Ov increasing up to 5%, the CeO2 exhibits a half-metallic properties. PMID:27554285

  4. Role of vacancies, light elements and rare-earth metals doping in CeO2

    PubMed Central

    Shi, H.; Hussain, T.; Ahuja, R.; Kang, T. W.; Luo, W.

    2016-01-01

    The magnetic properties and electronic structures of pure, doped and defective cerium oxide (CeO2) have been studied theoretically by means of ab initio calculations based on the density function theory (DFT) with the hybrid HF/DFT technique named PBE0. Carbon (C), nitrogen (N), phosphorus (P), sulphur (S), lanthanum (La) and praseodymium (Pr) doped in CeO2 and CeO2 containing oxygen vacancies (Ov) were considered. Our spin-polarized calculations show that C, N, Pr dopants and Ov defects magnetize the non-magnetic CeO2 in different degree. The optical band gap related to photocatalysis for pure CeO2, corresponding to the ultraviolet region, is reduced obviously by C, N, S, Pr impurities and oxygen vacancies, shifting to the visible region and even further to the infrared range. Especially, N-, S- and Pr-doped CeO2 could be used to photocatalytic water splitting for hydrogen production. As the concentration of Ov increasing up to 5%, the CeO2 exhibits a half-metallic properties. PMID:27554285

  5. Separation of Bk(IV) and Ce(IV) from trivalent transplutonium and rare-earth elements on ion exchangers in solutions of sulfuric acid

    SciTech Connect

    Guseva, L.I.; Stepushkina, V.V.

    1988-05-01

    The behavior of Am, Cm, Bk, Cf, Es, Ce, Eu, and Pr on anion exchangers and cation exchangers mixed with PbO/sub 2/ in solutions of sulfuric acid has been investigated. A significant difference between the distribution coefficients of Bk and Ce, on the one hand, and the remaining transplutonium elements and rare-earth elements, on the other hand, which has been attributed to the oxidation of the first two elements to the tetravalent state, has been discovered. Methods for the preconcentration and separation of Bk(IV) and Ce(IV) from the other transplutonium and rare-earth element son anion exchangers in 0.01-0.25 M H/sub 2/SO/sub 4/ solutions and on cation exchangers in 0.75-1.0 M H/sub 2/SO/sub 4/ solutions have been proposed.

  6. Separation of Bk(IV) and Ce(IV) from trivalent transplutonium and rare earth elements on ion exchange resins in solutions of sulfuric acid

    SciTech Connect

    Guseva, L.I.; Stepushkina, V.V.

    1987-11-01

    Th behavior of Am, Cm, Bk, Cf, Es, Ce, Eu, and Pr on an anion exchange resin and a cation exchange resin in a mixture with PbO/sub 2/ was investigated in sulfuric acid solutions. A substantial difference was detected in the distribution coefficients of Bk and Ce, on the one hand, and the remaining transplutonium and rare earth elements, on the other, associated with oxidation of the first two elements to the tetravalent state. Methods are proposed for the concentration and separation of Bk(IV) and Ce(IV) from the other transplutonium and rare earth elements on an anion exchange resin in solution of 0.01-0.25 M H/sub 2/SO/sub 4/ and a cation exchange resin in 0.75-1.0 M H/sub 2/SO/sub 4/.

  7. Scarcity of rare earth elements.

    PubMed

    de Boer, M A; Lammertsma, K

    2013-11-01

    Rare earth elements (REEs) are important for green and a large variety of high-tech technologies and are, therefore, in high demand. As a result, supply with REEs is likely to be disrupted (the degree of depends on the REE) in the near future. The 17 REEs are divided into heavy and light REEs. Other critical elements besides REEs, identified by the European Commission, are also becoming less easily available. Although there is no deficiency in the earth's crust of rare earth oxides, the economic accessibility is limited. The increased demand for REEs, the decreasing export from China, and geopolitical concerns on availability contributed to the (re)opening of mines in Australia and the USA and other mines are slow to follow. As a result, short supply of particularly terbium, dysprosium, praseodymium, and neodymium is expected to be problematic for at least the short term, also because they cannot be substituted. Recycling REEs from electronic waste would be a solution, but so far there are hardly any established REE recycling methods. Decreasing the dependency on REEs, for example, by identifying possible replacements or increasing their efficient use, represents another possibility. PMID:24009098

  8. Development of a Rare Earth Element Paleoproxy

    NASA Astrophysics Data System (ADS)

    Haley, B. A.; Klinkhammer, G. P.; McManus, J.

    2002-12-01

    The rare earth elements (REEs) have demonstrated considerable potential as paleoproxies for changes in seawater chemistry. However, their utilization in paleoceanographic investigations has been mainly limited to neodymium isotopic analyses in metalliferous deposits and fossil apatite. The goal of being able to use the entire group of elements in foraminiferal shells has proven difficult. The problem with analysis of these elements in this matrix stems mainly from: (1) the ability to clean the shells of diagenetic aberrations and (2) the paucity of REE data in the environment where forams obtain their primary signature. We recently measured pore water profiles of REEs using an interfaced Ion Chromatograph (IC) and Inductively Coupled Plasma Mass Spectrometer (ICP-MS) in a depth transect off the Coast of California, and a profile from off the Peru-Chile margin. The pore water results are surprising and will alter our view of REE marine geochemistry. For example, they call into question the traditional method of calculating a "Ce-anomaly." The profiles also show dramatic changes in REE concentrations and patterns with depth, and demonstrate that the REE signature preserved in epifaunal benthic versus infaunal foram species and diagenetically added phases should be easily identifiable. Preliminary REE results from forams cleaned via a recently developed flow-through technique will be shown and compared to matching pore water data. We will conclude by outlining the potential of foraminiferal REE content for paleoceanography that ranges from water mass tracer to proxies for organic carbon flux and oxygen concentration.

  9. Rare earth elements in the Amazon basin

    NASA Astrophysics Data System (ADS)

    Gerard, M.; Seyler, P.; Benedetti, M. F.; Alves, V. P.; Boaventura, G. R.; Sondag, F.

    2003-05-01

    The rare earth element (REE) concentrations of the dissolved and particulate fractions and bed sediment between Manaus and Santarém in the Amazon River, and in some major tributaries, were evaluated. A very important zone in the Amazon basin, the encontro das aguas area where the Rio Solimões and the Rio Negro meet, was especially sampled. Different size fractions were isolated by ultrafiltration. Water samples were collected at different stages of the mixing. Three groups of waters are distinguished: group I has a low pH (<5·5) and is represented by the Negro basin rivers; group II has alkalinity less than 0·2 meq l-1 and is represented by the Rios Tapajós and Trombetas; group III has high alkalinity (>0·2 meq l-1) and higher pH (>6·5) and is represented by the Madeira basin rivers, the Solimões and the Amazon. The highest dissolved REE concentration is in the Rio Negro and the lowest in the Rio Tapajós (dissolved REEs vary by more than a factor of ten). The solubility of REEs is pH dependent: in river waters with a pH < 6 the Ce concentration is twice that of La, whereas in rivers with a higher pH the concentrations of Ce and La are similar. Dissolved REE concentrations are positively correlated with the dissolved organic carbon. Correlations between Fe, Al, and La suggest that La is associated with Al (Fe)-rich organic matter and/or related to dissolved Fe-rich inorganic material. Dissolved REEs normalized to North American shale composite show an enrichment in intermediate/heavy REEs (from Eu to Er), except for the shields rivers (such as Rio Negro and Rio Trombetas). Both of them are depleted in heavy REEs and show a relative Ce enrichment. In contrast, for the Andeans rivers (such as Rio Solimões), light REEs are slightly depleted and a negative Ce relative anomaly occurs. The pattern of the Amazon River at Óbidos confirms the major influence of the Rios Negro and Solimões with REE fractionation. For the Rio Negro, 60 to 70% of REEs are

  10. Removal of Phosphorus in Metallurgical Silicon by Rare Earth Elements

    NASA Astrophysics Data System (ADS)

    Tang, Kai; Løvvik, Ole Martin; Safarian, Jafar; Ma, Xiang; Tangstad, Merete

    2014-09-01

    Removal of phosphorus in metallurgical silicon is one of the crucial steps for the production of solar grade Si feedstock. The possibility of doping rare earth elements for phosphorus removal has in this work been studied both theoretically and experimentally. Thermochemical properties of Ce, Nd, and Pr monophosphides have first been estimated by ab initio thermodynamic simulations based on density functional theory and the direct phonon method. The reliability of the first principles calculations was assessed by coupling with the phase diagram data of the Pr-P system. Equilibrium calculations confirmed the existence of stable rare earth monophosphides in solid silicon. Experimental investigations were then carried out, employing a high temperature resistance furnace. The Ce-doped silicon samples were examined by electron probe micro analyzer and inductively coupled plasma analysis. The efficiency of phosphorus removal by means of rare earth doping was discussed in detail in the paper.

  11. Systematic variation of rare-earth elements in cerium-earth minerals

    USGS Publications Warehouse

    Murata, K.J.; Rose, H.J., Jr.; Carron, M.K.; Glass, J.J.

    1957-01-01

    In a continuation of a study reported previously, rare-earth elements and thorium have been determined in monazite, allanite, cerite, bastnaesite, and a number of miscellaneous cerium-earth minerals. A quantity called sigma (???), which is the sum of the atomic percentages of La, Ce, and Pr, is proposed as an index of composition of all cerium-earth minerals with respect to the rare-earth elements. The value of ??? for all of the minerals analysed falls between 58 and 92 atomic per cent. Monazites, allanites, and cerites cover the entire observed range, whereas bastnaesites are sharply restricted to the range between 80 and 92 atomic per cent. The minimum value of ??? for a cerium-earth mineral corresponds to the smallest possible unit-cell size of the mineral. In monazite, this structurally controlled minimum value of ??? is estimated to be around 30 atomic per cent. Neodymium, because of its abundance, and yttrium, because of its small size, have dominant roles in contraction of the structure. In the other direction, the limit of variation in composition will be reached when lanthanum becomes the sole rare-earth element in a cerium-earth mineral. Cerium-earth minerals from alkalic rocks are all characterized by values of ??? greater than 80 atomic per cent, indicating that the processes that formed these rocks were unusually efficient in fractionating the rare-earth elements-efficient in the sense that a highly selected assemblage is produced without eliminating the bulk of these elements. Analyses of inner and outer parts of two large crystals of monazite from different deposits show no difference in ??? in one crystal and a slightly smaller value of ??? in the outer part of the other crystal compared to the inner part. The ??? of monazites from pegmatites that intrude genetically related granitic rocks in North Carolina is found to be either higher or lower than the ??? of monazites in the intruded host rock. These results indicate that the fractionation of the

  12. Uncovering the Global Life Cycles of the Rare Earth Elements

    PubMed Central

    Du, Xiaoyue; Graedel, T. E.

    2011-01-01

    The rare earth elements (REE) are a group of fifteen elements with unique properties that make them indispensable for a wide variety of emerging, critical technologies. Knowledge of the life cycles of REE remains sparse, despite the current heightened interest in their future availability. Mining is heavily concentrated in China, whose monopoly position and potential restriction of exports render primary supplies vulnerable to short and long-term disruption. To provide an improved perspective we derived the first quantitative life cycles (for the year 2007) for ten REE: lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), and yttrium (Y). Of these REE, Ce and Nd in-use stocks are highest; the in-use stocks of most REE show significant accumulation in modern society. Industrial scrap recycling occurs only from magnet manufacture. We believe there is no post-customer recycling of any of these elements. PMID:22355662

  13. Chemiluminescent Diagnostics of Free-Radical Processes in an Abiotic System and in Liver Cells in the Presence of Nanoparticles Based on Rare-Earth Elements nReVO4:Eu3+ (Re = Gd, Y, La) and CeO2

    NASA Astrophysics Data System (ADS)

    Averchenko, E. A.; Kavok, N. S.; Klochkov, V. K.; Malyukin, Yu. V.

    2014-11-01

    We have used luminol-dependent chemiluminescence with Fenton's reagent to study the effect of nanoparticles based on rare-earth elements of different sizes and shapes on free-radical processes in abiotic and biotic cell-free systems, and also in isolated cells in vitro. We have estimated the effects of rare-earth orthovanadate nanoparticles of spherical (GdYVO4:Eu3+, 1-2 nm), spindle-shaped (GdVO4:Eu3+, 25 ×8 nm), and rod-shaped (LaVO4:Eu3+, 57 × (6-8) nm) nanoparticles and spherical CeO2 nanoparticles (sizes 1-2 nm and 8-10 nm). We have shown that in contrast to the abiotic system, in which all types of nanoparticles exhibit antiradical activity, in the presence of biological material, extra-small spherical (1-2 nm) nanoparticles of both types exhibit pro-oxidant activity, and also enhance pro-oxidant induced oxidative stress (for the pro-oxidants hydrogen peroxide and tert-butyl hydroperoxide). The effect of rare-earth orthovanadate spindle and rod shaped nanoparticles in this system was neutral; a moderate antioxidant effect was exhibited by 8-10 nm CeO2 nanoparticles.

  14. Rare earth element content of cryptocrystalline magnesites of Konya, Turkey

    NASA Astrophysics Data System (ADS)

    Zedef, Veysel; Russell, Michael

    2016-04-01

    We examined the rare earth element content of several cryptocrystalline magnesites as well as hydromagnesite, host rock serpentinites, lake water and hot spring water from Turkey. Southwestern Turkey hosts cryptocrystalline magnesites, sedimentary magnesites with presently forming, biologically mediated hydromagnesites and travertines. Our results show the REE content of the minerals, rocks and waters are well below detection limits. One hydromagnesite sample from Lake Salda has slightly high La (2.38ppb), Ce (3.91 ppb) and Nd (1.68 ppb) when compared to other samples, but these are also still below detection limits of the method we followed.

  15. Rare earth element scavenging in seawater

    NASA Astrophysics Data System (ADS)

    Byrne, Robert H.; Kim, Ki-Hyun

    1990-10-01

    Examinations of rare earth element (REE) adsorption in seawater, using a variety of surface-types, indicated that, for most surfaces, light rare earth elements (LREEs) are preferentially adsorbed compared to the heavy rare earths (HREEs). Exceptions to this behavior were observed only for silica phases (glass surfaces, acid-cleaned diatomaceous earth, and synthetic SiO 2). The affinity of the rare earths for surfaces can be strongly affected by thin organic coatings. Glass surfaces which acquired an organic coating through immersion in Tampa Bay exhibited adsorptive behavior typical of organic-rich, rather than glass, surfaces. Models of rare earth distributions between seawater and carboxylate-rich surfaces indicate that scavenging processes which involve such surfaces should exhibit a strong dependence on pH and carbonate complexation. Scavenging models involving carboxylate surfaces produce relative REE abundance patterns in good general agreement with observed shale-normalized REE abundances in seawater. Scavenging by carboxylate-rich surfaces should produce HREE enrichments in seawater relative to the LREEs and may produce enrichments of lanthanum relative to its immediate trivalent neighbors. Due to the origin of distribution coefficients as a difference between REE solution complexation (which increases strongly with atomic number) and surface complexation (which apparently also increases with atomic number) the relative solution abundance patterns of the REEs produced by scavenging reactions can be quite complex.

  16. What about the rare-earth elements

    Technology Transfer Automated Retrieval System (TEKTRAN)

    There is insufficient understanding of the nutritional physiology of pecan trees and orchards; thus, affecting nutmeat yield and quality, disease resistance and alternate bearing. An analysis of the rare-earth element composition of pecan and related hickory cousins found that they hyperaccumulate ...

  17. Isotopic fractionation of rare earth elements in geochemical samples

    NASA Astrophysics Data System (ADS)

    Ishibashi, T.; Ohno, T.

    2015-12-01

    The isotopic composition of Rare Earth Elements(REEs) can be fractionated through various physical and chemical reactions in nature [1]. The isotopic variations of REEs occurring naturally has a potentially significant influence in geochemical research fields. The REEs has key features that their chemical similarities and gradual changes of ionic radius, which may help us to understand the mechanisms of isotopic variations of REEs in nature. Among the REEs, geochemical and physicochemical features of Ce, which could be presence as the tetravalent state, be anomalous, and oxidation state of Ce can change by reflecting the redox conditions of the environment. Therefore, the study of the difference in the degree of isotopic fractionation between Ce and other REEs may provide information on the redox conditions. In this study, we developed a new separation method to determine the mass-dependent isotopic fractionations of REEs in geochemical samples, and examined the optimum concentration of hydrochloric acid for the separation. The samples were decomposed by a mixture of acids, then REEs were separated as a group from major elements using cation exchange resin columns and RE Spec resin. The separations within the REEs group were carried out using Ln2Spec resin. For the recovery of La, Ce, Pr, and Nd, 0.1 M HCl was used, and for isolation of Sm, Eu, and Gd, 0.25 M HCl was used. Then, 0.6 M HCl was used for separation of Tb, and Dy, 1 M HCl was used for separation of Ho, Y, and Er, finally, Tm, Yb, and Lu were collected using 2 M HCl. The yields of all REEs were enough to examine isotopic fractionation in geochemical samples. [1] Ohno and Hirata,Analytical Sciences, 29, 271, 2013

  18. Standard reference water samples for rare earth element determinations

    USGS Publications Warehouse

    Verplanck, P.L.; Antweiler, R.C.; Nordstrom, D.K.; Taylor, H.E.

    2001-01-01

    Standard reference water samples (SRWS) were collected from two mine sites, one near Ophir, CO, USA and the other near Redding, CA, USA. The samples were filtered, preserved, and analyzed for rare earth element (REE) concentrations (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) by inductively coupled plasma-mass spectrometry (ICP-MS). These two samples were acid mine waters with elevated concentrations of REEs (0.45-161 ??g/1). Seventeen international laboratories participated in a 'round-robin' chemical analysis program, which made it possible to evaluate the data by robust statistical procedures that are insensitive to outliers. The resulting most probable values are reported. Ten to 15 of the participants also reported values for Ba, Y, and Sc. Field parameters, major ion, and other trace element concentrations, not subject to statistical evaluation, are provided.

  19. Interactions between exogenous rare earth elements and phosphorus leaching in packed soil columns

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Rare earth elements (REEs) increasingly used in agriculture as an amendment for crop growth may help to lessen environmental losses of phosphorus (P) from heavily fertilized soils. The vertical transport characteristics of P and REEs, lanthanum (La), neodymium (Nd), samarium (Sm), and cerium (Ce), w...

  20. Effects of rare-earth substitution in the oxyarsenides REFeAsO (RE=Ce, Pr, Nd, Sm, Gd) and CeNiAsO by X-ray photoelectron and absorption spectroscopy

    SciTech Connect

    Blanchard, Peter E.R.; Cavell, Ronald G.; Mar, Arthur

    2010-08-16

    X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge spectroscopy (XANES) have been applied to examine the electronic structure of the rare-earth transition-metal oxyarsenides REFeAsO (RE=Ce, Pr, Nd, Sm, Gd) and CeNiAsO. Within the metal-arsenic layer [MAs], the bonding character is predominantly covalent and the As atoms are anionic, as implied by the small energy shifts in the M 2p and As 3d XPS spectra. Within the rare-earth-oxygen layer [REO], the bonding character is predominantly ionic, as implied by the similarity of the O 1s binding energies to those in highly ionic oxides. Substitution with a smaller RE element increases the O 1s binding energy, a result of an enhanced Madelung potential. The Ce 3d XPS and Ce L{sub 3}-edge XANES spectra have lineshapes and energies that confirm the presence of trivalent cerium in CeFeAsO and CeNiAsO. A population analysis of the valence band spectrum of CeNiAsO supports the formal charge assignment [Ce{sup 3+}O{sup 2-}][Ni{sup 2+}As{sup 3-}].

  1. Rare earth element systematics in hydrothermal fluids

    SciTech Connect

    Michard, A. )

    1989-03-01

    Rare earth element concentrations have been measured in hydrothermal solutions from geothermal fields in Italy, Dominica, Valles Caldera, Salton Sea and the Mid-Atlantic Ridge. The measured abundances show that hydrothermal activity is not expected to affect the REE balance of either continental or oceanic rocks. The REE enrichment of the solutions increases when the pH decreases. High-temperature solutions (> 230{degree}C) percolating through different rock types may show similar REE patterns.

  2. Biogeochemistry of the rare-earth elements with particular reference to hickory trees

    USGS Publications Warehouse

    Robinson, W.O.; Bastron, H.; Murata, K.J.

    1958-01-01

    Hickory trees concentrate the rare-earth elements in their leaves to a phenomenal degree and may contain as much as 2300 p.p.m. of total rare earths based on the dry weight of the leaves. The average proportions of the individual elements (atomic percent of the total rare-earth elements) in the leaves are: Y 36, La 16, Ce 14, Pr 2, Nd 20, Sm 1, Eu 0.7, Gd 3, Tb 0.6, Dy 3, Ho 0.7, Er 2, Tm 0.2, Yb 1, and Lu 0.2. The similarity in the proportions of the rare-earth elements in the leaves and in the exchange complex of the soil on which the hickory trees grow indicates that the trees do not fractionate the rare earths appreciably. The variation of the rare-earth elements in the leaves and soils can be explained generally in terms of the relative abundance of the cerium group and the yttrium group, except for the element cerium. The large fluctuations in the proportion of cerium [Ce/(La + Nd) atomic ratios of 0.16 to 0.86] correlate with oxidation-reduction conditions in the soil profile. The substitution of dilute H2SO3 for dilute HC1 in the determination of available rare-earth elements brings about a large increase in the proportion of cerium that is extracted from an oxygenated subsoil. These relationships strongly suggest that quadrivalent cerium is present in oxygenated subsoil and is less available to plants than the other rare-earth elements that do not undergo such a change in valence. A few parts per billion of rare-earth elements have been detected in two samples of ground water. ?? 1958.

  3. Rare earth elements and permanent magnets (invited)

    NASA Astrophysics Data System (ADS)

    Dent, Peter C.

    2012-04-01

    Rare earth (RE) magnets have become virtually indispensible in a wide variety of industries such as aerospace, automotive, electronics, medical, and military. RE elements are essential ingredients in these high performance magnets based on intermetallic compounds RECo5, RE2TM17 (TM: transition metal), and RE2TM14B. Rare earth magnets are known for their superior magnetic properties—high induction, and coercive force. These properties arise due to the extremely high magnetocrystalline anisotropy made possible by unique 3d-4f interactions between transition metals and rare earths. For more than 40 years, these magnets remain the number one choice in applications that require high magnetic fields in extreme operating conditions—high demagnetization forces and high temperature. EEC produces and specializes in RECo5 and RE2TM17 type sintered magnets. Samarium and gadolinium are key RE ingredients in the powder metallurgical magnet production processes which include melting, crushing, jet milling, pressing, sintering, and heat treating. The magnetic properties and applications of these magnets will be discussed. We will also briefly discuss the past, current, and future of the permanent magnet business. Currently, over 95% of all pure rare earth oxides are sourced from China, which currently controls the market. We will provide insights regarding current and potential new magnet technologies and designer choices, which may mitigate rare earth supply chain issues now and into the future.

  4. Loparite, a rare-earth ore (Ce, Na, Sr, Ca)(Ti, Nb, Ta, Fe+3)O3

    USGS Publications Warehouse

    Hedrick, J.B.; Sinha, S.P.; Kosynkin, V.D.

    1997-01-01

    The mineral loparite (Ce, NA, Sr, Ca)(Ti, Nb, Ta, Fe+3)O3 is the principal ore of the light-group rare-earth elements (LREE) in Russia. The complex oxide has a perovskite (ABO3) structure with coupled substitutions, polymorphism, defect chemistry and a tendency to become metamict. The A site generally contains weakly bonded, easily exchanged cations of the LREE, Na and Ca. The B site generally contains smaller, highly charged cations of Ti, Nb or Fe+3. Mine production is from Russia's Kola Peninsula. Ore is beneficiated to produce a 95% loparite concentrate containing 30% rare-earth oxides. Loparite concentrate is refined by either a chlorination process or acid decomposition process to recover rare-earths, titanium, niobium and tantalum. Rare-earths are separated by solvent extraction and selective precipitation/dissolution. The concentrate is processed at plants in Russia, Estonia and Kazakstan.

  5. Rare Earth Element Partition Coefficients from Enstatite/Melt Synthesis Experiments

    NASA Technical Reports Server (NTRS)

    Schwandt, Craig S.; McKay, Gordon A.

    1997-01-01

    Enstatite (En(80)Fs(19)Wo(01)) was synthesized from a hypersthene normative basaltic melt doped at the same time with La, Ce, Nd, Sm, Eu, Dy, Er, Yb and Lu. The rare earth element concentrations were measured in both the basaltic glass and the enstatite. Rare earth element concentrations in the glass were determined by electron microprobe analysis with uncertainties less than two percent relative. Rare earth element concentrations in enstatite were determined by secondary ion mass spectrometry with uncertainties less than five percent relative. The resulting rare earth element partition signature for enstatite is similar to previous calculated and composite low-Ca pigeonite signatures, but is better defined and differs in several details. The partition coefficients are consistent with crystal structural constraints.

  6. Note: Portable rare-earth element analyzer using pyroelectric crystal.

    PubMed

    Imashuku, Susumu; Fuyuno, Naoto; Hanasaki, Kohei; Kawai, Jun

    2013-12-01

    We report a portable rare-earth element analyzer with a palm-top size chamber including the electron source of a pyroelectric crystal and the sample stage utilizing cathodoluminescence (CL) phenomenon. The portable rare-earth element analyzer utilizing CL phenomenon is the smallest reported so far. The portable rare-earth element analyzer detected the rare-earth elements Dy, Tb, Er, and Sm of ppm order in zircon, which were not detected by scanning electron microscopy-energy dispersive X-ray spectroscopy analysis. We also performed an elemental mapping of rare-earth elements by capturing a CL image using CCD camera. PMID:24387481

  7. Note: Portable rare-earth element analyzer using pyroelectric crystal

    SciTech Connect

    Imashuku, Susumu Fuyuno, Naoto; Hanasaki, Kohei; Kawai, Jun

    2013-12-15

    We report a portable rare-earth element analyzer with a palm-top size chamber including the electron source of a pyroelectric crystal and the sample stage utilizing cathodoluminescence (CL) phenomenon. The portable rare-earth element analyzer utilizing CL phenomenon is the smallest reported so far. The portable rare-earth element analyzer detected the rare-earth elements Dy, Tb, Er, and Sm of ppm order in zircon, which were not detected by scanning electron microscopy-energy dispersive X-ray spectroscopy analysis. We also performed an elemental mapping of rare-earth elements by capturing a CL image using CCD camera.

  8. Anthropogenic Cycles of Rare Earth Elements

    NASA Astrophysics Data System (ADS)

    Du, X.; Graedel, T. E.

    2009-12-01

    This research will develop quantitatively resolved anthropogenic cycles and in-use stocks for the rare earth metals specifically cerium, lanthanum and dysprosium in Japan, China, and the U.S. for the year of 2007. Rare earth elements (REE) is a group of 17 scare metals widely used in a growing number of emerging technologies and have been in high demand for emerging technologies as raw materials during past the three decades. New market participants from newly industrializing countries, primarily China, have had strong impacts on the demand of share. Consequently, the importance to sustain a reliable, steady, uninterrupted supply on global market triggered comprehensive research to recognize and understand the life cycles of rare earths. Moreover, because China plays a dominant role in mining production since 1990, it requires the assessment for the countries, which are almost completely dependent on imports from China with respect to rare earth resources. The study aims to analyze the flows and stocks of rare earth elements individually as elemental form in spite of their natural geological co-occurrence and mixed composition in applications. By applying the method of Material Flow Analysis (MFA) work has been done on evaluating current and historical flows of specific technologically significant materials, for example, copper, zinc, nickel, etc., determining the stocks available in different types of reservoirs (e.g., lithosphere, in-use) and the flows among the reservoirs, developing scenarios of possible futures of metal use, and assessing the environmental and policy implications of the results. Therefore, REE as a new target deserves inclusion because of its potential demand-supply conflict and importance to secure the competitive advantage of technical innovation in future. This work will generate a quantitatively resolved anthropogenic life cycle and in-use stocks for REE for the main target countries for a chosen year, 2007, providing flows and stocks from

  9. Siderophile elements and the earth's formation

    NASA Technical Reports Server (NTRS)

    Jones, J. H.; Capobianco, C. J.; Drake, M. J.; O'Neill, Hugh

    1992-01-01

    Two comments on a work by Murthy (1991) concerning the abundances of siderophile elements in the earth's mantle are presented. In the first comment it is asserted that the basis of Murthy's extrapolation is the assumption that the Gibbs free energy change for the partitioning reaction is independent of temperature, and as this is generally not a valid assumption thermodynamically, and as this is contradicted by most experimental data, the issue of mantle siderophile elements remains unresolved. In the second comment it is asserted that the extrapolation method used by Murthy does not appear to be valid thermodynamically, and that an extrapolation based on generally accepted thermodynamic assumptions yields different results. In a reply, Murthy takes issue with the comments.

  10. Tipping elements in the Earth's climate system

    SciTech Connect

    Lenton, T.M.; Held, H.; Lucht, W.; Rahmstorf, S.; Kriegler, E. |; Hall, J.W.; Schellnhuber, H.J. |

    2008-02-12

    The term 'tipping point' commonly refers to a critical threshold at which a tiny perturbation can qualitatively alter the state or development of a system. Here the authors introduce the term 'tipping element' to describe large-scale components of the Earth system that may pass a tipping point. They critically evaluate potential policy-relevant tipping elements in the climate system under anthropogenic forcing, drawing on the pertinent literature and a recent international workshop to compile a short list, and they assess where their tipping points lie. An expert elicitation is used to help rank their sensitivity to global warming and the uncertainty about the underlying physical mechanisms. Then the authors explain how, in principle, early warning systems could be established to detect the proximity of some tipping points.

  11. The geochemistry of rare earth elements in the Amazon River estuary

    SciTech Connect

    Shokovitz, E.R. )

    1993-05-01

    The estuarine geochemistry of rare earth elements (REEs) was studied using samples collected in the Amazon River estuary from the AmasSeds (Amazon Shelf SEDiment Study) cruise of August 1989. Extensive removal of dissolved (0.22 [mu]m filtered) trivalent REEs from river water occurs in the low (0--6) salinity region. Removal by the salt-induced coagulation of river colloids leads to fractionation among the REE(III) series; the order of removal is light REEs > middle REEs > heavy REEs. There also is the enhanced removal of Ce (relative to trivalent La and Nd) in the low salinity (0--6) zone and in the zone of high biological activity. This is the first field observation of strong Ce removal associated with coagulation of river colloids and biological productivity. The argument is made that the decrease in the Ce anomaly across a biological front is caused by biologically mediated oxidation of Ce(III) to Ce(IV). Coagulation of river colloids and biologically mediated oxidation of Ce(III) lead to fractionation of REE(III) and redox modification of Ce. These processes result in the REE composition becoming fractionated relative to the Amazon River water and crust and more evolved toward the REE composition of the oceans. This study implies that reactions in estuaries play significant, yet poorly understood roles in controlling the REE composition and Ce anomaly of the oceans. 46 refs., 9 figs., 2 tabs.

  12. Ternary rare-earth iron arsenides RE12Fe57.5As41 (RE = La, Ce).

    PubMed

    Stoyko, Stanislav S; Blanchard, Peter E R; Mar, Arthur

    2010-03-01

    The rare-earth iron arsenides RE(12)Fe(57.5)As(41) (RE = La, Ce) have been prepared by direct reactions of the elements in the presence of a Sn flux. Analysis of single-crystal X-ray diffraction data reveals that they adopt a new orthorhombic structure type (Pearson symbol oP236, space group Pmmn, Z = 2; a = 10.8881(9) A, b = 25.753(2) A, c = 12.5436(10) A for RE = La; a = 10.8376(8) A, b = 25.639(2) A, c = 12.4701(9) A for RE = Ce). In this metal-rich arsenide, the complex three-dimensional network (derived from 4 RE, 24 Fe, and 17 As sites) can be described as being built from unusual wavelike layers of connected As-centered trigonal prisms. Five of the Fe sites are partially occupied. The electronic structure of these compounds was probed through core-line X-ray photoelectron spectra. Magnetic susceptibility measurements indicated ferromagnetic ordering at T(C) = 125 and 95 K for the La and Ce compounds, respectively. Electrical resistivity measurements on single crystals of Ce(12)Fe(57.5)As(41) showed metallic behavior with a prominent transition that coincides closely with the ferromagnetic ordering temperature. PMID:20128600

  13. Site-preference and valency for rare-earth sites in (R-Ce)(2)Fe14B magnets

    SciTech Connect

    Alam, A; Khan, M; McCallum, RW; Johnson, DD

    2013-01-28

    Rare-earth (R) permanent magnets of R2Fe14B have technological importance due to their high energy products, and they have two R-sites (Wyckoff 4f and 4g, with four-fold multiplicity) that affect chemistry and valence. Designing magnetic behavior and stability via alloying is technologically relevant to reduce critical (expensive) R-content while retaining key properties; cerium, an abundant (cheap) R-element, offers this potential. We calculate magnetic properties and Ce site preference in (R1-xCex)(2)Fe14B [R = La, Nd] using density functional theory (DFT) methods-including a DFT+U scheme to treat localized 4f-electrons. Fe moments compare well with neutron data-almost unaffected by Hubbard U, and weakly affected by spin-orbit coupling. In La2Fe14B, Ce alloys for 0 <= x <= 1 and prefers smaller R(4f) sites, as observed, a trend we find unaffected by valence. Whereas, in Nd2Fe14B, Ce is predicted to have limited alloying (x <= 0.3) with a preference for larger R(4g) sites, resulting in weak partial ordering and segregation. The Curie temperatures versus x for (Nd, Ce) were predicted for a typical sample processing and verified experimentally. (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4789527

  14. Rare earth elements materials production from apatite ores

    NASA Astrophysics Data System (ADS)

    Anufrieva, A. V.; Andrienko, O. S.; Buynovskiy, A. S.; Makaseev, Y. N.; Mazov, I. N.; Nefedov, R. A.; Sachkov, V. I.; Stepanova, O. B.; Valkov, A. V.

    2016-01-01

    The paper deals with the study of processing apatite ores with nitric acid and extraction of the rare earth elements. The rare earth elements can be successfully separated and recovered by extraction from the nitrate- phosphate solution, being an tributyl phosphate as extraction agent. The developed scheme of the processing apatite concentrate provides obtaining rare earth concentrates with high qualitative characteristics.

  15. [Application of ICP-MS to Detect Rare Earth Elements in Three Economic Macroalgaes in China].

    PubMed

    Zhao, Yan-fang; Shang, De-rong; Zhai, Yu-xiu; Ning, Jin-song; Ding, Hai-yan; Sheng, Xiao-feng

    2015-11-01

    In order to investigate the content and distribution of rare earth elements (REE) in main economic macroalgaes in our country, fifteen rare earth elements in three economic macroalgaes (including 30 samples of kelp, 30 samples of laver and 15 samples of Enteromorpha) were detected using ICP-MS method. Results showed that the total content of REE in different species of macroalgaes was different. The highest total content of REE was in Enteromorpha (16,012.0 ng · g⁻¹), while in kelp and laver, the total REE was similar for two macroalgaes (3887.4 and 4318.1 ng · g⁻¹ respectively). The content of fifteen rare earth elements in kelp ranged from 7.9 to 1496.4 ng · g⁻¹; in laver, it ranged from 8.2 to 1836.6 ng · g⁻¹. For Enteromorpha, the concentration of 15 rare earth elements were between 19.2 and 6014.5 ng · g⁻¹. In addition, the content and distribution of different rare earth elements in different macroalgaes was also different. For kelp, the highest content of REE was Ce (1 496.4 ng · g⁻¹), and the second was La (689.1 ng · g⁻¹). For laver, the highest was Y (1836.6 ng · g⁻¹), and the second was Ce (682.2 ng · g⁻¹). For Enteromorpha, the highest was Ce (6014.5 ng · g⁻¹), and the second was La (2902.9 ng · g⁻¹). Present results also showed that three macroalgaes accumulated the light rare earth elements much more than the high rare earth elements. The light rare earth elements occupied 90.9%, 87.3% and 91.1% for kelp, laver and Enteromorpha respectively. The result that the Enteromorpha had high content of rare earth elements could provide important support for opening new research directions for the utilization of Enteromorpha. PMID:26978935

  16. Rare earth elements in river waters

    NASA Technical Reports Server (NTRS)

    Goldstein, Steven J.; Jacobsen, Stein B.

    1988-01-01

    To characterize the input to the oceans of rare earth elements (REE) in the dissolved and the suspended loads of rivers, the REE concentrations were measured in samples of Amazon, Indus, Mississippi, Murray-Darling, and Ohio rivers and in samples of smaller rivers that had more distinct drainage basin lithology and water chemistry. It was found that, in the suspended loads of small rivers, the REE pattern was dependent on drainage basin geology, whereas the suspended loads in major rivers had relatively uniform REE patterns and were heavy-REE depleted relative to the North American Shale composite (NASC). The dissolved loads in the five major rivers had marked relative heavy-REE enrichments, relative to the NASC and the suspended material, with the (La/Yb)N ratio of about 0.4 (as compared with the ratio of about 1.9 in suspended loads).

  17. Calculation of binary phase diagrams between the actinide elements, rare earth elements, and transition metal elements

    SciTech Connect

    Selle, J E

    1992-06-26

    Attempts were made to apply the Kaufman method of calculating binary phase diagrams to the calculation of binary phase diagrams between the rare earths, actinides, and the refractory transition metals. Difficulties were encountered in applying the method to the rare earths and actinides, and modifications were necessary to provide accurate representation of known diagrams. To calculate the interaction parameters for rare earth-rare earth diagrams, it was necessary to use the atomic volumes for each of the phases: liquid, body-centered cubic, hexagonal close-packed, and face-centered cubic. Determination of the atomic volumes of each of these phases for each element is discussed in detail. In some cases, empirical means were necessary. Results are presented on the calculation of rare earth-rare earth, rare earth-actinide, and actinide-actinide diagrams. For rare earth-refractory transition metal diagrams and actinide-refractory transition metal diagrams, empirical means were required to develop values for the enthalpy of vaporization for rare earth elements and values for the constant (C) required when intermediate phases are present. Results of using the values determined for each element are presented.

  18. Reducing the detection limits of rare earth elements in steels

    SciTech Connect

    Raskevich, V.K.; Maiboroda, I.K.; Frishberg, A.A.; Panfilova, S.Ya.

    1986-12-01

    Chemical and chemicospectral analysis methods make it possible to determine rare-earth elements (REE) reliably in steels, but they are time-consuming and laborious. X-ray fluorescence methods are also characterized by the complicated procedure of preparing standard and production specimens for analysis. In this paper, the authors attempt to develop a spectrographic method of determining the REEs in the steel using standard equipment. The authors prepare synthetic standard specimens for determining Ce, Nd, La, Pr, and Y in steels of various grades by adding titrated solutions of the salts of the determined elements to the powder of the steel without REE with subsequent evaporation, drying, and mixing. The steels were ground by the mechanical method. On the basis of the resulting detection limits and analysis accuracy, the proposed method can be recommended for inspection of the technological process in melting steels and for preparation of standard specimens in the plant. The method is 5-7 times faster than the chemicospectral method.

  19. Earth rotation changes since -500 CE driven by ice mass variations

    NASA Astrophysics Data System (ADS)

    Hay, Carling; Mitrovica, Jerry X.; Morrow, Eric; Kopp, Robert E.; Huybers, Peter; Alley, Richard B.

    2016-08-01

    We predict the perturbation to the Earth's length-of-day (LOD) over the Common Era using a recently derived estimate of global sea-level change for this time period. We use this estimate to derive a time series of "clock error", defined as the difference in timing of two clocks, one based on a theoretically invariant time scale (terrestrial time) and one fixed to Earth rotation (universal time), and compare this time series to millennial scale variability in clock error inferred from ancient eclipse records. Under the assumption that global sea-level change over the Common Era is driven by ice mass flux alone, we find that this flux can reconcile a significant fraction of the discrepancies between clock error computed assuming constant slowing of Earth's rotation and that inferred from eclipse records since 700 CE. In contrast, ice mass flux cannot reconcile the temporal variability prior to 700 CE.

  20. Google Earth locations of USA and seafloor hydrothermal vents with associated rare earth element data

    DOE Data Explorer

    Andrew Fowler

    2016-02-10

    Google Earth .kmz files that contain the locations of geothermal wells and thermal springs in the USA, and seafloor hydrothermal vents that have associated rare earth element data. The file does not contain the actual data, the actual data is available through the GDR website in two tier 3 data sets entitled "Compilation of Rare Earth Element Analyses from US Geothermal Fields and Mid Ocean Ridge (MOR) Hydrothermal Vents" and "Rare earth element content of thermal fluids from Surprise Valley, California"

  1. Determination of Rare Earth Elements in Human Sperm and Association with Semen Quality.

    PubMed

    Marzec-Wróblewska, Urszula; Kamiński, Piotr; Łakota, Paweł; Ludwikowski, Grzegorz; Szymański, Marek; Wasilow, Karolina; Stuczyński, Tomasz; Buciński, Adam; Jerzak, Leszek

    2015-08-01

    The aim of the present study was to measure lanthanum (La), cerium (Ce), europium (Eu), and gadolinium (Gd) concentrations in human semen and correlate the results with sperm quality. The median semen content of La was 19.5 µg kg(-1) dry weight (dw) (range 2.27-269), of Ce was 41.9 µg kg(-1) dw (range 4.52 to 167), of Eu was 0.68 µg kg(-1) dw (range 0.06-1.95), of Gd was 3.19 µg kg(-1) dw (range 0.38-12.0), and of calcium (Ca) was 4063 mg kg(-1) dw (range 484-17,191). Concentrations of La, Ce, Eu, Gd, and Ca were significantly lower in nondrinkers' semen than in semen from drinkers. Significant differences were detected between La, Ce, Eu, Gd, and Ca concentrations in semen from nondrinkers and moderate drinkers. Concentrations of La, Ce, and Gd in semen of short-term smokers were significantly lower than those in extremely long-term smokers. Significant differences were also detected between La concentration in semen from a group of short-term smokers and that of a group of long-term smokers. Positive correlations were found between La, Ce, Eu, Gd, and Ca concentrations in semen. La, Ce, Gd, and Ca concentrations in semen were positively associated with progressive motility and percentage of normal spermatozoa. Positive correlations were found between Ca and sperm concentration. Concentrations of La, Ce, and Gd were negatively associated with sperm concentration, whilst Ca concentration was negatively associated with volume of ejaculate. At the examined level, La, Ce, Eu, and Gd did not affect sperm quality, whereas alcohol consumption and smoking might have increased the level of rare earth elements in semen. PMID:25762379

  2. Cerium redox cycles and rare earth elements in the Sargasso Sea

    SciTech Connect

    Sholkovitz, E.R.; Schneider, D.L. )

    1991-10-01

    Two profiles of the rare earth elements (REEs) are reported for the upper water column of the Sargasso Sea. The trivalent-only REEs have remarkably constant concentrations in the upper 500m of an April 1989 profile and in the upper 200m of a May 1989 profile. In contrast, Ce concentrations decrease smoothly with increasing depth. In April 1989 Ce decreases from 15.7 pmol/kg at 20 m to 5.1 pmol/kg at 750 m. Cerium, which has Redox transformations in seawater, behaves anomalously with respect to its REE(III) neighbors. While both dissolved Ce and Mn have elevated concentrations in the upper 200m, their vertical gradients are distinctly different. In contrast to Mn, which reaches a minimum dissolved concentration near the zone (150-250 m) of a particulate Mn maximum, Ce is being removed both near this zone and to depths of at least 750m. These new profiles indicate that Ce is involved in an upper ocean redox cycle. This interpretation is consistent with the MOFFETT (1990) incubation tracer experiments on the same May 1989 seawater. He showed that Ce(III) oxidation is biologically mediated, probably light inhibited, increases with depth, and 3-4 times slower than Mn(II) oxidation in the 100-200 m zone. CERoclines provide new information into the fine scale zonation of redox process operating in the upper columns of oligotrophic oceans.

  3. NEW RARE EARTH ELEMENT ABUNDANCE DISTRIBUTIONS FOR THE SUN AND FIVE r-PROCESS-RICH VERY METAL-POOR STARS

    SciTech Connect

    Sneden, Christopher; Lawler, James E.; Den Hartog, Elizabeth A.; Cowan, John J.; Ivans, Inese I. E-mail: jelawler@wisc.edu E-mail: cowan@nhn.ou.edu

    2009-05-15

    We have derived new abundances of the rare earth elements Pr, Dy, Tm, Yb, and Lu for the solar photosphere and for five very metal-poor, neutron-capture r-process-rich giant stars. The photospheric values for all five elements are in good agreement with meteoritic abundances. For the low-metallicity sample, these abundances have been combined with new Ce abundances from a companion paper, and reconsideration of a few other elements in individual stars, to produce internally consistent Ba, rare earth, and Hf (56 {<=} Z {<=} 72) element distributions. These have been used in a critical comparison between stellar and solar r-process abundance mixes.

  4. Rare-earth element based permanent magnets: a theoretical investigation

    NASA Astrophysics Data System (ADS)

    Chouhan, Rajiv K.; Paudyal, Durga

    Permanent magnetic materials with large magnetization and high magnetocrystalline anisotropy are important for technical applications. In this context rare-earth (R) element based materials are good candidates because of their localized 4 f electrons. The 4 f crystal field splitting provides large part of magnetic anisotropy depending upon the crystal environment. The d spin orbit coupling of alloyed transition metal component provides additional anisotropy. RCo5 and its derivative R2Co17 are known compounds for large magnetic anisotropy. Here we have performed electronic structure calculations to predict new materials in this class by employing site substitutions. In these investigations, we have performed density functional theory including on-site electron correlation (DFT +U) and L-S coupling calculations. The results show that the abundant Ce substitution in R sites and Ti/Zr substitutions in some of the Co sites help reduce criticality without substantially affecting the magnetic moment and magnetic anisotropy in these materials. This work is supported by the Critical Materials Institute, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Advanced Manufacturing Office.

  5. Ce-MXRF: the power of separation with bench top element sensitive detection

    SciTech Connect

    Miller, T. C.; Joseph, M. R.; Havrilla, G. J.

    2002-01-01

    Capillary electrophoresis (CE) is a proven separation technique that offers highly efficient separation, rapid analysis, and minute sample consumption. When combined with a element specific detection scheme, it can be used for chemical speciation of biologically and environmentally relevant species such as metal containing proteins. In this study, a new tool was developed for separation and elemental detection. Specifically, a simple CE apparatus was constructed using a thin-walled fused Si capillary and interfaced with a bench top micro x-ray fluorescence (MXRF) system. X-ray excitation and detection of the separated sample volumes was performed using an EDAX Eagle II micro x-ray fluorescence system equipped with a Rh target excitation source and a SiLi detector. It was demonstrated that the system could be used for the separation and detection of two metals from one another, specifically Cu{sup 2+} and Co{sup 2+}. Free Co{sup 2+} could also be isolated from Co{sup 2+} bound to cyanocobalamin (Vitamin B-12). Other systems that were explored were the separation of two organics, ferritin from cyanocobalamin as well as the separation of the different Cu and Zn isoforms of metallothinein. CE-MXRF was also used to separate the important serum isoforms of transferrin. Direct comparisons were made between CE-MXRF system and other elemental separation techniques such as CE-PIXE, CE-synchrotron-XRF, and CE-ICPMS.

  6. Rare earth magnetism in CeFeAsO: a single crystal study

    NASA Astrophysics Data System (ADS)

    Jesche, A.; Krellner, C.; de Souza, M.; Lang, M.; Geibel, C.

    2009-10-01

    Single crystals of CeFeAsO, large enough to study the anisotropy of the magnetic properties, were grown by an optimized Sn-flux technique. The high quality of our single crystals is apparent from the highest residual resistivity ratio (RRR)≈12, reported among undoped RFeAsO compounds (R=rare earth) as well as sharp anomalies in resistivity, specific heat, C(T), and thermal expansion at the different phase transitions. The magnetic susceptibility χ(T) presents a large easy-plane anisotropy consistent with the lowest crystal electric field doublet having a dominant Γ6 character. Curie-Weiss-like susceptibilities for magnetic field parallel and perpendicular to the crystallographic c-axis do not reveal an influence of a staggered field on the Ce site induced by magnetic ordering of the Fe. Furthermore, the standard signatures for antiferromagnetic order of Ce at TN4f=3.7 K observed in χ(T) and C(T) are incompatible with a Zeeman splitting Δ≈10 K of the CEF ground state doublet at low temperature due to the Fe-magnetic order as previously proposed. Our results can be reconciled with the earlier observation by assuming a comparatively stronger effect of the Ce-Ce exchange leading to a reduction of this Zeeman splitting below 15 K.

  7. Rare earth elements in Hamersley BIF minerals

    NASA Astrophysics Data System (ADS)

    Alibert, Chantal

    2016-07-01

    Minerals from the Hamersley banded iron formation, Western Australia, were analyzed for Y and rare earth elements (YREEs) by laser ablation ICP-MS to investigate diagenetic pathways, from precursor phases to BIF minerals. One group of apatites carries the seawater REE signature, giving evidence that P and REEs, thoroughly scavenged from the water column by Si-ferrihydrite particles, were released upon microbial Fe3+ reductive dissolution of Si-ferrihydrite in pore-water and finally sequestered mainly in authigenic apatite. The absence of fractionation between apatite and seawater suggests that REE were first incorporated into an amorphous calcium phosphate as fully hydrated cations, i.e. as outer-sphere complexes. The iron oxides and carbonates carry only a small fraction of the whole-rock REE budget. Their REE patterns are distinctly enriched in Yb and show some M-type tetrad effect consistent with experimental Kd(REE) between solid and saline solution with low carbonate ion concentrations. It is deduced that hematite formed at an incipient stage of Fe2+-catalyzed dissolution of Si-ferrihydrite, via a dissolution-reprecipitation pathway. The REE pattern of greenalite, found as sub-micron particles in quartz in a chert-siderite sample, is consistent with its authigenic origin by precipitation in pore-water after dissolution of a small amount of Si-ferrihydrite. Magnetite carries very low YREEs (ppb-level), has an homogeneous pattern distinctly enriched in the mid-REEs compared to hematite, and includes a late population depleted in light-REEs, Ba and As. Magnetite forming aggregates and massive laminae is tentatively interpreted as reflecting some fluid-aided hematite-magnetite re-equilibration or transformation at low-grade metamorphic temperatures.

  8. Substitution of Nd with other rare earth elements in melt spun Nd2Fe14B magnets

    NASA Astrophysics Data System (ADS)

    Brown, D. N.; Lau, D.; Chen, Z.

    2016-05-01

    This is a contemporary study of rapidly quenched Nd1.6X0.4Fe14B magnetic materials (where X= Nd, Y, Ce, La, Pr, Gd and Ho). A 20% substitution of the Nd component from Nd2Fe14B can bring about some commercial advantage. However, there will be some compromise to the magnetic performance. Light rare earth elements are definitely more abundant (Y, Ce, La) than the heavier rare earth elements, but when they are included in RE2Fe14B magnets they tend to lower magnetic performance and thermal stability. Substituting heavy rare earth elements (Gd, Ho) for Nd in Nd2Fe14B improves the thermal stability of magnets but causes a loss in magnet remanence.

  9. Correlation of XANES features with the scintillation efficiencies of Ce doped alkaline earth lithium silicate glasses

    SciTech Connect

    Blanchard, D.L.; Sunberg, D.S.; Craig, R.A.; Bliss, M.; Weber, M.J.

    1994-11-01

    Cerium-activated, lithium-silicate glasses are widely used as thermal neutron detectors because of their versatility, robustness and low cost. The glasses convert the energy of the neutrons to visible light pulses that may be counted. This process, scintillation, is generally thought to be composed of three steps: ionization, energy transfer, and luminescence. If defects are present, they can trap the excitations, altering the scintillation output. These features have been discussed previously. The presence of magnesium in these glasses increases scintillation efficiency, but as previously observed the effect drops by a factor greater than 2.5 with substitution through the series of alkaline earths. Here, cerium activated glasses of composition 20Li{sub 2}O{center_dot}15MO{center_dot}64.4SiO{sub 2}{center_dot}0.6Ce{sub 3}O{sub 3} (where m is Mg, Ca, Sr, or Ba) exhibit scintillation efficiencies that vary by more than a factor of 2.5 with the alkaline earth. Previous work has suggested a correlation between the microstructure of these glasses and scintillation efficiency. Measurements of the Ce L{sub III} x-ray absorption edge in the Mg, Ca and Sr glasses display a feature near the absorption edge that is suggestive of the presence of Ce{sup 4+}. The area of this peak is, in fact, correlated with the scintillation efficiency of the glass. The amount of Ce{sup 4+} indicated by the intensity of this feature is, however, too high to be a permanent population. The authors suspect that the feature is a transient phenomenon related to creation of Ce{sup 4+} and trapped electrons due to photoionization by the x-ray beam.

  10. Rare earth elements (REEs): effects on germination and growth of selected crop and native plant species.

    PubMed

    Thomas, Philippe J; Carpenter, David; Boutin, Céline; Allison, Jane E

    2014-02-01

    The phytotoxicity of rare earth elements (REEs) is still poorly understood. The exposure-response relationships of three native Canadian plant species (common milkweed, Asclepias syriaca L., showy ticktrefoil, Desmodium canadense (L.) DC. and switchgrass, Panicum virgatum L.) and two commonly used crop species (radish, Raphanus sativus L., and tomato, Solanum lycopersicum L.) to the REEs lanthanum (La), yttrium (Y) and cerium (Ce) were tested. In separate experiments, seven to eight doses of each element were added to the soil prior to sowing seeds. Effects of REE dose on germination were established through measures of total percent germination and speed of germination; effects on growth were established through determination of above ground biomass. Ce was also tested at two pH levels and plant tissue analysis was conducted on pooled samples. Effects on germination were mostly observed with Ce at low pH. However, effects on growth were more pronounced, with detectable inhibition concentrations causing 10% and 25% reductions in biomass for the two native forb species (A. syriaca and D. canadense) with all REEs and on all species tested with Ce in both soil pH treatments. Concentration of Ce in aboveground biomass was lower than root Ce content, and followed the dose-response trend. From values measured in natural soils around the world, our results continue to support the notion that REEs are of limited toxicity and not considered extremely hazardous to the environment. However, in areas where REE contamination is likely, the slow accumulation of these elements in the environment could become problematic. PMID:23978671

  11. Alkali element constraints on Earth-Moon relations

    NASA Technical Reports Server (NTRS)

    Norman, M. D.; Drake, M. J.; Jones, J. H.

    1994-01-01

    Given their range of volatilities, alkali elements are potential tracers of temperature-dependent processes during planetary accretion and formation of the Earth-Moon system. Under the giant impact hypothesis, no direct connection between the composition of the Moon and the Earth is required, and proto-lunar material does not necessarily experience high temperatures. Models calling for multiple collisions with smaller planetesimals derive proto-lunar materials mainly from the Earth's mantle and explicitly invoke vaporization, shock melting and volatility-related fractionation. Na/K, K/Rb, and Rb/Cs should all increase in response to thermal volatization, so theories which derive the Moon substantially from Earth's mantle predict these ratios will be higher in the Moon than in the primitive mantle of the Earth. Despite the overall depletion of volatile elements in the Moon, its Na/K and K/Rb are equal to or less than those of Earth. A new model presented here for the composition of Earth's continental crust, a major repository of the alkali elements, suggests the Rb/Cs of the Moon is also less than that of Earth. Fractionation of the alkali elements between Earth and Moon are in the opposite sense to predictions based on the relative volatilities of these elements, if the Moon formed by high-T processing of Earth's mantle. Earth, rather than the Moon, appears to carry a signature of volatility-related fractionation in the alkali elements. This may reflect an early episode of intense heating on Earth with the Moon's alkali budget accreting from cooler material.

  12. Earth, Air, Fire and Water in Our Elements

    ERIC Educational Resources Information Center

    Lievesley, Tara

    2007-01-01

    The idea that everything is made of the four "elements", earth, air, fire and water, goes back to the ancient Greeks. In this article, the author talks about the origins of ideas about the elements. The author provides an account that attempts to summarise thousands of years of theoretical development of the elements in a thousand words or so.

  13. Rare earth element association with foraminifera

    NASA Astrophysics Data System (ADS)

    Roberts, Natalie L.; Piotrowski, Alexander M.; Elderfield, Henry; Eglinton, Timothy I.; Lomas, Michael W.

    2012-10-01

    Neodymium isotopes are becoming widely used as a palaeoceanographic tool for reconstructing the source and flow direction of water masses. A new method using planktonic foraminifera which have not been chemically cleaned has proven to be a promising means of avoiding contamination of the deep ocean palaeoceanographic signal by detrital material. However, the exact mechanism by which the Nd isotope signal from bottom waters becomes associated with planktonic foraminifera, the spatial distribution of rare earth element (REE) concentrations within the shell, and the possible mobility of REE ions during changing redox conditions, have not been fully investigated. Here we present REE concentration and Nd isotope data from mixed species of planktonic foraminifera taken from plankton tows, sediment traps and a sediment core from the NW Atlantic. We used multiple geochemical techniques to evaluate how, where and when REEs become associated with planktonic foraminifera as they settle through the water column, reside at the surface and are buried in the sediment. Analyses of foraminifera shells from plankton tows and sediment traps between 200 and 2938 m water depth indicate that only ˜20% of their associated Nd is biogenically incorporated into the calcite structure. The remaining 80% is associated with authigenic metal oxides and organic matter, which form in the water column, and remain extraneous to the carbonate structure. Remineralisation of these organic and authigenic phases releases ions back into solution and creates new binding sites, allowing the Nd isotope ratio to undergo partial equilibration with the ambient seawater, as the foraminifera fall through the water column. Analyses of fossil foraminifera shells from sediment cores show that their REE concentrations increase by up to 10-fold at the sediment-water interface, and acquire an isotopic signature of bottom water. Adsorption and complexation of REE3+ ions between the inner layers of calcite contributes

  14. A major light rare-earth element (LREE) resource in the Khanneshin carbonatite complex, southern Afghanistan

    USGS Publications Warehouse

    Tucker, Robert D.; Belkin, Harvey E.; Schulz, Klaus J.; Peters, Stephen G.; Horton, Forrest; Buttleman, Kim; Scott, Emily R.

    2012-01-01

    The rapid rise in world demand for the rare-earth elements (REEs) has expanded the search for new REE resources. We document two types of light rare-earth element (LREE)-enriched rocks in the Khanneshin carbonatite complex of southern Afghanistan: type 1 concordant seams of khanneshite-(Ce), synchysite-(Ce), and parisite-(Ce) within banded barite-strontianite alvikite, and type 2 igneous dikes of coarse-grained carbonatite, enriched in fluorine or phosphorus, containing idiomorphic crystals of khanneshite-(Ce) or carbocernaite. Type 1 mineralized barite-strontianite alvikite averages 22.25 wt % BaO, 4.27 wt % SrO, and 3.25 wt % ∑ LREE2O3 (sum of La, Ce, Pr, and Nd oxides). Type 2 igneous dikes average 14.51 wt % BaO, 5.96 wt % SrO, and 3.77 wt % ∑ LREE2O3. A magmatic origin is clearly indicated for the type 2 LREE-enriched dikes, and type 1 LREE mineralization probably formed in the presence of LREE-rich hydrothermal fluid. Both types of LREE mineralization may be penecontemporaneous, having formed in a carbonate-rich magma in the marginal zone of the central vent, highly charged with volatile constituents (i.e., CO2, F, P2O5), and strongly enriched in Ba, Sr, and the LREE. Based on several assumptions, and employing simple geometry for the zone of LREE enrichment, we estimate that at least 1.29 Mt (million metric tonnes) of LREE2O3 is present in this part of the Khanneshin carbonatite complex.

  15. Magnetization switching of rare earth orthochromite CeCrO{sub 3}

    SciTech Connect

    Cao, Yiming; Cao, Shixun Ren, Wei; Feng, Zhenjie; Yuan, Shujuan; Kang, Baojuan; Zhang, Jincang; Lu, Bo

    2014-06-09

    We report the synthesis of single phase rare earth orthochromite CeCrO{sub 3} and its magnetic properties. A canted antiferromagnetic transition with thermal hysteresis at T = 260 K is observed, and a magnetic compensation (zero magnetization) near 133 K is attributed to the antiparallel coupling between Ce{sup 3+} and Cr{sup 3+} moments. At low temperature, field induced magnetization reversal starting from 43 K for H = 1.2 kOe reveals the spin flip driven by Zeeman energy between the net moments and the applied field. These findings may find potential uses in magnetic switching devices such as nonvolatile magnetic memory which facilitates two distinct states of magnetization.

  16. Siderophile and chalcophile element abundances in oceanic basalts, Pb isotope evolution and growth of the earth's core

    NASA Technical Reports Server (NTRS)

    Newsom, H. E.; White, W. M.; Jochum, K. P.; Hofmann, A. W.

    1986-01-01

    The hypothesis that the mantle Pb isotope ratios reflect continued extraction of Pb into the earth's core over geologic time is evaluated by studying the depeletion of chalcophile and siderophile elements in the mantle. Oceanic basalt samples are analyzed in order to determine the Pb, Sr, and Nd isotropic compositions and the abundances of siderophile and chalcophile elements and incompatible lithophile elements. The data reveal that there is no systematic variation of siderophile or chalcophile element abundances relative to abundances of lithophile elements and the Pb/Ce ratio of the mantle is constant. It is suggested that the crust formation involves nonmagmatic and magmatic processes.

  17. Rare earth element distributions in recent and fossil apatite: implications for paleoceanography and stratigraphy

    SciTech Connect

    Wright, J.

    1985-01-01

    Rare earth element (REE) distributions in biogenic apatite were determined in over 200 samples from Cambrian to the Recent. Nondestructive instrumental neutron activation analysis techniques were adapted for analysis of low-mass microfossil samples. Tests for chemical contamination, interspecies, interlaboratory and interexperiment variations show that there is no fractionation of REE, so that ratios of rare earths are consistent throughout the entire group of samples. The REE signature of biogenic apatite is acquired after deposition but only at the sediment-water interface and is characteristic of the redox state of the environment of deposition. This original environmental signature is retained through subsequent burial and diagenesis. Cerium has been shown to be the rare earth element that is sensitive to oxidation-reduction variations in marine waters. This cerium variation is stated mathematically and called Ce/sub anom/. Comparison of Ce/sub anom/ in fish debris from different modern redox environments shows that values > -0.10 occur in fish debris deposited under reducing conditions, whereas Ce/sub anom/ values <-0.10 are obtained under oxidizing conditions. Paleoredox studies of Ce/sub anom/ of fossil apatite of conodonts, fish debris and inarticulate brachiopods indicate that significant shifts in the overall redox balance of seawater occurred in ancient oceans. Cambrian through Silurian seas were dominated by anoxia, followed by a gradual change to oxidizing conditions in the Devonian. Oceans remained generally oxidizing throughout the Carboniferous and Lower Permian. In the Upper Permian and Lower Triassic anoxic conditions were again prevalent. This was followed by a return to an oxidizing oceanic environment in the Upper Triassic.

  18. Geochemistry of the rare earth elements in ferromanganese nodules from DOMES Site A, northern equatorial Pacific

    USGS Publications Warehouse

    Calvert, S.E.; Piper, D.Z.; Baedecker, P.A.

    1987-01-01

    The distribution of rare earth elements (REE) in ferromanganese nodules from DOMES Site A has been determined by instrumental neutron activation methods. The concentrations of the REE vary markedly. Low concentrations characterize samples from a depression (the valley), in which Quaternary sediments are thin or absent; high concentrations are found in samples from the surrounding abyssal hills (the highlands) where the Quaternary sediment section is relatively thick. Moreover, the valley nodules are strongly depleted in the light trivalent REE (LREE) and Ce compared with nodules from the highlands, some of the former showing negative Ce anomalies. The REE abundances in the nodules are strongly influenced by the REE abundances in coexisting bottom water. Some controls on the REE chemistry of bottom waters include: a) the more effective removal of the LREE relative to the HREE from seawater because of the greater degree of complexation of the latter elements with seawater ligands, b) the very efficient oxidative scavenging of Ce on particle surfaces in seawater, and c) the strong depletion of both Ce and the LREE in, or a larger benthic flux of the HREE into, the Antarctic Bottom Water (AABW) which flows through the valley. The distinctive REE chemistry of valley nodules is a function of their growth from geochemically evolved AABW. In contrast, the REE chemistry of highland nodules indicates growth from a local, less evolved seawater source. ?? 1987.

  19. Adsorption and oxidation of elemental mercury over Ce-MnOx/Ti-PILCs.

    PubMed

    He, Chuan; Shen, Boxiong; Chen, Jianhong; Cai, Ji

    2014-07-15

    A series of innovative Ce-Mn/Ti-pillared-clay (Ce-Mn/Ti-PILC) catalysts combining the advantages of PILCs and Ce-Mn were investigated for elemental mercury (Hg0) capture at 100-350 °C in the absence of HCl in the flue gas. The fresh and used catalysts were characterized by scanning electron microscopy (SEM), nitrogen adsorption-desorption, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The catalyst characterization indicated that the 6%Ce-6%MnOx/Ti-PILC catalyst possessed a large specific surface area and high dispersion of Ce and Mn on the surface. The experimental results indicated that the 6%Ce-6%MnOx/Ti-PILC catalyst exhibited high Hg0 capture (>90%) at 100-350 °C. During the first stage of the reaction, the main Hg0 capture mechanism for the catalyst was adsorption. As the reaction proceeded, the Hg0 oxidation ability was substantially enhanced. Both the hydroxyl oxygen and the lattice oxygen on the surface of the catalysts participated in Hg0 oxidation. At a low temperature (150 °C), the hydroxyl oxygen and lattice oxygen from Ce4+→Ce3+ and Mn3+→Mn2+ on the surface contributed to Hg0 oxidation. However, at a high temperature (250 °C), the hydroxyl oxygen and lattice oxygen from Mn4+→Mn3+ contributed to Hg0 oxidation. Hg0 oxidation was preferred at a high temperature. The 6%Ce-6%MnOx/Ti-PILC catalyst was demonstrated to a good Hg0 adsorbent and catalytic oxidant in the absence of HCl in the flue gas. PMID:24956201

  20. Extraction of rare-earth elements from nitric solutions by phosphoryl-containing podands

    SciTech Connect

    Turanov, A.N.; Karandashev, V.K.; Baulin, V.E.

    1999-11-01

    The extraction of microquantities of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y from HNO{sub 3} solutions by phosphoryl-containing podands of various structures has been studied.. It has been found that the maximum extraction of rare earth elements is exhibited by reagents containing one ether oxygen atom in the molecule, bound to diphenylphosphoryl or ditolylphosphoryl groups by methylene and o-phenylene fragments. The structure of these reagents is best suited for the polydentate coordination of the ligand and the conditions of a chelate complex formation. The effect of HNO{sub 3} concentration in the aqueous phase and that of the nature of an organic diluent on the extraction of rare earth elements and Y are considered. Stoichiometric of the extracted complexes has been determined and the extraction constants calculated.

  1. Rare earth elements recycling from waste phosphor by dual hydrochloric acid dissolution.

    PubMed

    Liu, Hu; Zhang, Shengen; Pan, Dean; Tian, Jianjun; Yang, Min; Wu, Maolin; Volinsky, Alex A

    2014-05-15

    This paper is a comparative study of recycling rare earth elements from waste phosphor, which focuses on the leaching rate and the technical principle. The traditional and dual dissolution by hydrochloric acid (DHA) methods were compared. The method of dual dissolution by hydrochloric acid has been developed. The Red rare earth phosphor (Y0.95Eu0.05)2O3 in waste phosphor is dissolved during the first step of acid leaching, while the Green phosphor (Ce0.67Tb0.33MgAl11O19) and the Blue phosphor (Ba0.9Eu0.1MgAl10O17) mixed with caustic soda are obtained by alkali sintering. The excess caustic soda and NaAlO2 are removed by washing. The insoluble matter is leached by the hydrochloric acid, followed by solvent extraction and precipitation (the DHA method). In comparison, the total leaching rate of the rare earth elements was 94.6% by DHA, which is much higher than 42.08% achieved by the traditional method. The leaching rate of Y, Eu, Ce and Tb reached 94.6%, 99.05%, 71.45%, and 76.22%, respectively. DHA can decrease the consumption of chemicals and energy. The suggested DHA method is feasible for industrial applications. PMID:24681591

  2. Uranium and rare earth elements in CO 2-rich waters from Vals-les-Bains (France)

    NASA Astrophysics Data System (ADS)

    Michard, Annie; Beaucaire, Catherine; Michard, Gil

    1987-04-01

    Waters from springs at Vals-les-Bains result from the mixing of a CO 2-rich, highly mineralized water with dilute, shallow subsurface water. Total content of dissolved species vary from 5 mmol/1 to 100 mmol/1. For many elements, mixing of these waters is non-linear (non-conservative) and further water-rock reactions take place. The pH is controlled by CO 2 outgassing, redox conditions are controlled by both the iron hydroxide-siderite buffer and the introduction of oxygen with shallow subsurface waters. Among the major elements, concentrations of Ca, Mg, Mn, Fe, are related to mixing, CO 2 outgassing and carbonate precipitation. Uranium shows a complex behaviour controlled by carbonate complexing, redox conditions, mixing of waters and leaching from the rocks. The 234U /238U activity ratio is near secular equilibrium. In the more dilute waters, dissolved rare earth element (REE) patterns are almost flat with a slight negative Eu anomaly. In the concentrated waters, heavy rare earth elements (Gd-Yb, HREE) are strongly enriched relative to light rare earth elements (Ce-Eu, LREE). We relate the enrichment in HREE to water chemistry and to complexing with carbonate species.

  3. Rare earth elements in synthetic zircon. 1. synthesis, and rare earth element and phosphorus doping.

    SciTech Connect

    Hanchar, J. M.; Finch, R. J.; Hoskin, W. O.; Watson, E. B.; Cherniak, D. J.; Mariano, A. N.; Chemical Engineering; George Washington Univ.; Univ. of Canterbury; Australian National Univ.; Rensselaer Polytechnic Inst.

    2001-05-01

    Sedimentary mineral assemblages commonly contain detrital zircon crystals as part of the heavy-mineral fraction. Age spectra determined by U-Pb isotopic analysis of single zircon crystals within a sample may directly image the age composition--but not the chemical composition--of the source region. Rare earth element (REE) abundances have been measured for zircons from a range of common crustal igneous rock types from different tectonic environments, as well as kimberlite, carbonatite, and high-grade metamorphic rocks, to assess the potential of using zircon REE characteristics to infer the rock types present in sediment source regions. Except for zircon with probable mantle affinities, zircon REE abundances and normalized patterns show little intersample and intrasample variation. To evaluate the actual variation in detrital zircon REE composition in a true sediment of known mixed provenance, zircons from a sandstone sample from the Statfjord Formation (North Sea) were analyzed. Despite a provenance including high-grade metasediment and granitoids and a range in zircon age of 2.82 b.y., the zircon REEs exhibit a narrow abundance range with no systematic differences in pattern shape. These evidences show zircon REE patterns and abundances are generally not useful as indicators of provenance.

  4. Rare earth element systematics of fossil bone revealed by LA-ICPMS analysis

    NASA Astrophysics Data System (ADS)

    Herwartz, Daniel; Tütken, Thomas; Jochum, Klaus Peter; Sander, P. Martin

    2013-02-01

    Intra-bone rare earth element (REE) fractionation trends were studied by LA-ICPMS analysis to put constraints on (1) the mechanisms controlling REE fractionation within fossil bones; (2) the relative timing of REE uptake in various parts of fossil bone and (3) the origin of REE in fossil bones. We have evaluated REE bone profiles across 54 fossil bones from a broad range of well-characterised taphonomic settings ranging in age from Triassic to early Medieval. REE patterns and concentration gradients are highly variable and intra-bone fractionation trends in (La/Yb)N vs. (La/Sm)N space of few specimens cover almost the entire range previously observed for bulk samples. Intra-bone variability of Ce anomalies, as well as variable Y/Ho and (La/La∗)N is also observed. Sometimes, diagenetic fluids with fractionated, HREE enriched compositions have entered the bone from the marrow cavity, producing secondary REE uptake profiles. Theoretical intra-bone fractionation trends, modelled using lattice strain theory, concur with most REE data but some trends cannot be modelled using realistic boundary conditions. This fact, as well as the occurence of positive and negative Ce anomalies within the same fossil sample, hint towards changing REE compositions of diagenetic fluids over the timescales of REE uptake. Because apparent Ce anomalies frequently evolve over bone profiles and Ce anomalies can be inherited from previous fractionation events, Ce anomalies are a highly ambiguous tracer for constraining ambient redox conditions. In general, bioapatite REE signatures may not always reliably reflect ambient taphonomic or redox conditions and diagenetic fluid compositions. Therefore REE patterns and Ce anomalies of fossil bones must be interpreted cautiously as they vary spatially within skeletal remains and are affected by intra-bone fractionation processes as well as changing compositions of the diagenetic fluid.

  5. Bioleaching of rare earth elements from monazite sand.

    PubMed

    Brisson, Vanessa L; Zhuang, Wei-Qin; Alvarez-Cohen, Lisa

    2016-02-01

    Three fungal strains were found to be capable of bioleaching rare earth elements from monazite, a rare earth phosphate mineral, utilizing the monazite as a phosphate source and releasing rare earth cations into solution. These organisms include one known phosphate solubilizing fungus, Aspergillus niger ATCC 1015, as well as two newly isolated fungi: an Aspergillus terreus strain ML3-1 and a Paecilomyces spp. strain WE3-F. Although monazite also contains the radioactive element Thorium, bioleaching by these fungi preferentially solubilized rare earth elements over Thorium, leaving the Thorium in the solid residual. Adjustments in growth media composition improved bioleaching performance measured as rare earth release. Cell-free spent medium generated during growth of A. terreus strain ML3-1 and Paecilomyces spp. strain WE3-F in the presence of monazite leached rare earths to concentrations 1.7-3.8 times those of HCl solutions of comparable pH, indicating that compounds exogenously released by these organisms contribute substantially to leaching. Organic acids released by the organisms included acetic, citric, gluconic, itaconic, oxalic, and succinic acids. Abiotic leaching with laboratory prepared solutions of these acids was not as effective as bioleaching or leaching with cell-free spent medium at releasing rare earths from monazite, indicating that compounds other than the identified organic acids contribute to leaching performance. PMID:26332985

  6. MaRGEE: Move and Rotate Google Earth Elements

    NASA Astrophysics Data System (ADS)

    Dordevic, Mladen M.; Whitmeyer, Steven J.

    2015-12-01

    Google Earth is recognized as a highly effective visualization tool for geospatial information. However, there remain serious limitations that have hindered its acceptance as a tool for research and education in the geosciences. One significant limitation is the inability to translate or rotate geometrical elements on the Google Earth virtual globe. Here we present a new JavaScript web application to "Move and Rotate Google Earth Elements" (MaRGEE). MaRGEE includes tools to simplify, translate, and rotate elements, add intermediate steps to a transposition, and batch process multiple transpositions. The transposition algorithm uses spherical geometry calculations, such as the haversine formula, to accurately reposition groups of points, paths, and polygons on the Google Earth globe without distortion. Due to the imminent deprecation of the Google Earth API and browser plugin, MaRGEE uses a Google Maps interface to facilitate and illustrate the transpositions. However, the inherent spatial distortions that result from the Google Maps Web Mercator projection are not apparent once the transposed elements are saved as a KML file and opened in Google Earth. Potential applications of the MaRGEE toolkit include tectonic reconstructions, the movements of glaciers or thrust sheets, and time-based animations of other large- and small-scale geologic processes.

  7. Applications of the Space-Time Conservation Element and Solution Element (CE/SE) Method to Computational Aeroacoustic Benchmark Problems

    NASA Technical Reports Server (NTRS)

    Wang, Xiao-Yen; Himansu, Ananda; Chang, Sin-Chung; Jorgenson, Philip C. E.

    2000-01-01

    The Internal Propagation problems, Fan Noise problem, and Turbomachinery Noise problems are solved using the space-time conservation element and solution element (CE/SE) method. The problems in internal propagation problems address the propagation of sound waves through a nozzle. Both the nonlinear and linear quasi 1D Euler equations are solved. Numerical solutions are presented and compared with the analytical solution. The fan noise problem concerns the effect of the sweep angle on the acoustic field generated by the interaction of a convected gust with a cascade of 3D flat plates. A parallel version of the 3D CE/SE Euler solver is developed and employed to obtain numerical solutions for a family of swept flat plates. Numerical solutions for sweep angles of 0, 5, 10, and 15 deg are presented. The turbomachinery problems describe the interaction of a 2D vortical gust with a cascade of flat-plate airfoils with/without a downstream moving grid. The 2D nonlinear Euler Equations are solved and the converged numerical solutions are presented and compared with the corresponding analytical solution. All the comparisons demonstrate that the CE/SE method is capable of solving aeroacoustic problems with/without shock waves in a simple and efficient manner. Furthermore, the simple non-reflecting boundary condition used in the CE/SE method which is not based on the characteristic theory works very well in 1D, 2D and 3D problems.

  8. Ocean particle chemistry: The fractionation of rare earth elements between suspended particles and seawater

    SciTech Connect

    Sholkovitz, E.R. ); Landing, W.M.; Lewis, B.L. )

    1994-03-01

    Sargasso Sea suspended particles were sequentially digested with three chemical treatments (acetic acid, mild HCl/HNO[sub 3], and HF/HNO[sub 3]/HCl in a bomb). The latter two treatments dissolve detrital minerals, while the acetic acid removes surface coatings (organic matter and Mn oxides). The rare earth element (REE) composition of the surface coatings, in marked contrast to the crust-like REE composition of the two detrital phases, is extensively fractionated with respect to both filtered seawater and the crust. Surface coatings are responsible for the removal and fractionation of REEs from seawater and, as such, play a key role in the marine geochemical cycles of trace elements. Relative to seawater, the surface coatings are systematically enriched tenfold across the trivalent REEs from Lu to La and develop large positive Ce-anomalies. The Ce-anomalies of the coatings switch from being negative (seawater-like) in the upper 100 m to being strongly positive at greater depths. The ingrowth of Ce and LREEs on particle surfaces reflects the in situ oxidation of dissolved Ce(III) to particulate Ce(IV), and the preferential removal of LREE(III)s over HREE(III)s. REEs(III) fractionation of this type is consistent with particle/solution models. Both processes appear to be related to the in situ formation of Mn oxide particles from the oxidation of dissolved Mn(II) in the upper 200 m of the water column. Preferential removal of LREEs in the upper waters is countered by their preferential release at depth due to remineralization of surface coatings on particles. A new method is explored for estimating the residence time of suspended particles by combining Ce concentration data of dissolved and surface-bound phases with the Ce(III) oxidation rate measurements of MOFFETT (1990). A Ce-based residence time of thirteen days is similar in magnitude to the value calculated from U-[sup 234]Th disequilibria in the Sargasso Sea.

  9. Modeling rammed earth wall using discrete element method

    NASA Astrophysics Data System (ADS)

    Bui, T.-T.; Bui, Q.-B.; Limam, A.; Morel, J.-C.

    2016-03-01

    Rammed earth is attracting renewed interest throughout the world thanks to its "green" characteristics in the context of sustainable development. Several research studies have thus recently been carried out to investigate this material. Some of them attempted to simulate the rammed earth's mechanical behavior by using analytical or numerical models. Most of these studies assumed that there was a perfect cohesion at the interface between earthen layers. This hypothesis proved to be acceptable for the case of vertical loading, but it could be questionable for horizontal loading. To address this problem, discrete element modeling seems to be relevant to simulate a rammed earth wall. To our knowledge, no research has been conducted thus far using discrete element modeling to study a rammed earth wall. This paper presents an assessment of the discrete element modeling's robustness for rammed earth walls. Firstly, a brief description of the discrete element modeling is presented. Then the parameters necessary for discrete element modeling of the material law of the earthen layers and their interfaces law following the Mohr-Coulomb model with a tension cut-off and post-peak softening were given. The relevance of the model and the material parameters were assessed by comparing them with experimental results from the literature. The results showed that, in the case of vertical loading, interfaces did not have an important effect. In the case of diagonal loading, model with interfaces produced better results. Interface characteristics can vary from 85 to 100% of the corresponding earthen layer's characteristics.

  10. Alkali elements in the Earth's core: Evidence from enstatite meteorites

    NASA Technical Reports Server (NTRS)

    Lodders, K.

    1995-01-01

    The abundances of alkali elements in the Earth's core are predicted by assuming that accretion of the Earth started from material similar in composition to enstatite chondrites and that enstatite achondrites (aubrites) provide a natural laboratory to study core-mantle differentiation under extremely reducing conditions. If core formation on the aubrite parent body is comparable with core formation on the early Earth, it is found that 2600 (+/- 1000) ppm Na, 550 (+/- 260) ppm K, 3.4 (+/- 2.1) ppm Rb, and 0.31 (+/- 0.24) ppm Cs can reside in the Earth's core. The alkali-element abundances are consistent with those predicted by independent estimates based on nebula condensation calculations and heat flow data.

  11. SEPARATION OF TRANSURANIC ELEMENTS FROM RARE EARTH COMPOUNDS

    DOEpatents

    Kohman, T.P.

    1961-11-21

    A process of separating neptunium and plutonium values from rare earths and alkaline earth fission products present on a solid mixed actinide carrier (Th or U(IV) oxalate or fluoride) --fission product carrier (LaF/sub 3/, CeF/sub 3/, SrF/sub 2/, CaF/sub 2/, YF/sub 3/, La oxalate, cerous oxalate, Sr oxalate, Ca oxalate or Y oxalate) by extraction of the actinides at elevated temperature with a solution of ammonium fluoride and/or ammonium oxalate is described. Separation of the fission-product-containing carriers from the actinide solution formed and precipitation of the neptunium and plutonium from the solution with mineral acid are also accomplished. (AEC)

  12. Magnetic Nanofluid Rare Earth Element Extraction Process Report, Techno Economic Analysis, and Results for Geothermal Fluids

    DOE Data Explorer

    Pete McGrail

    2016-03-14

    This GDR submission is an interim technical report and raw data files from the first year of testing on functionalized nanoparticles for rare earth element extraction from geothermal fluids. The report contains Rare Earth Element uptake results (percent removal, mg Rare Earth Element/gram of sorbent, distribution coefficient) for the elements of Neodymium, Europium, Yttrium, Dysprosium, and Cesium. A detailed techno economic analysis is also presented in the report for a scaled up geothermal rare earth element extraction process. All rare earth element uptake testing was done on simulated geothermal brines with one rare earth element in each brine. The rare earth element uptake testing was conducted at room temperature.

  13. Determination of thorium and of rare earth elements in cerium earth minerals and ores

    USGS Publications Warehouse

    Carron, M.K.; Skinner, D.L.; Stevens, R.E.

    1955-01-01

    The conventional oxalate method for precipitating thorium and the rare earth elements in acid solution exhibits definite solubilities of these elements. The present work was undertaken to establish conditions overcoming these solubilities and to find optimum conditions for precipitating thorium and the rare earth elements as hydroxides and sebacates. The investigations resulted in a reliable procedure applicable to samples in which the cerium group elements predominate. The oxalate precipitations are made from homogeneous solution at pH 2 by adding a prepared solution of anhydrous oxalic acid in methanol instead of the more expensive crystalline methyl oxalate. Calcium is added as a carrier. Quantitative precipitation of thorium and the rare earth elements is ascertained by further small additions of calcium to the supernatant liquid, until the added calcium precipitates as oxalate within 2 minutes. Calcium is removed by precipitating the hydroxides of thorium and rare earths at room temperature by adding ammonium hydroxide to pH > 10. Thorium is separated as the sebacate at pH 2.5, and the rare earths are precipitated with ammonium sebacate at pH 9. Maximum errors for combined weights of thorium and rare earth oxides on synthetic mixtures are ??0.6 mg. Maximum error for separated thoria is ??0.5 mg.

  14. Rare earth elements in soils from selected areas on the Island of Hawaii

    SciTech Connect

    Barnard, W.M.; Halbig, J.B.

    1985-07-01

    Fifty soil samples for the wet, windward (east) side and dry, leeward (west) side of the Island of Hawaii were analyzed for La, Ce, Sm, Eu, Yb, and Lu by neutron activation/gamma-ray spectroscopic analysis. Data on concentrations in each sample are listed and analyzed statistically for soil samples collected from the western slope of Kohala Mountain, the western coastal plain of Mauna Kea, and the Northeastern coastal plain of Maunal Loa. Rare earth element (REE) concentrations are two to six times greater in soils from the western, dry side of the island, and good statistical correlation is exhibited among the samples for pairs of individual REEs. In the organic-rich soils of the east side, correlations are poor but are markedly improved when sample weights are adjusted for weight due to organic matter and water in soil colloids. If the mean compositions of selected rock samples from the Hawaii Reference Suite are representative of the compositions of the parent materials, REEs in the soils are moderately enriched (up to two times, based on oven-dry weights). Rare earth element concentrations in the island's western soils are as much as two times greater than the mean REE values of common sedimentary rocks worldwide; however, they are well within the concentration ranges of soils of continental origin. The eastern soils tend to have less La and Ce, but similar amounts of the middle and heavy REEs.

  15. Miocene Coral Skeleton Rare Earth Element Patterns Reflect River Discharge

    NASA Astrophysics Data System (ADS)

    Mertz-Kraus, R.; Brachert, T. C.; Jochum, K. P.

    2010-12-01

    Rare Earth Element (REE) patterns of modern coral skeletons usually reflect the REE composition of ambient seawater which is characterized by heavy REE enriched relative to light REE with NASC (North American Shale Composite) normalized La/Lu ratios of typically <0.4. The REE concentration in coral aragonite is enriched by 3 to 4 orders of magnitude compared to ambient seawater. Here we report trace element data including REE of coral skeletons of Late Miocene age (~9 Ma, Tortonian) from Crete (Eastern Mediterranean). Analyses were done using a 213 nm Nd:YAG laser coupled to an Element2 ICP-MS along the growth axis of the coral skeletons. The profiles show that Ba/Ca ratios have a seasonally induced pattern with high values around the winter months which are identified by δ18O analyses. REE/Ca ratios co-vary with Ba/Ca ratios. Since the Ba/Ca ratio is a proxy used to monitor river discharge, the co-variation suggests the REE/Ca ratio to be a proxy of comparable quality. NASC-normalized REE patterns of the Tortonian corals have negative Ce anomalies like modern corals. However, the Tortonian corals have REE patterns highly enriched in LREE with (La/Lu)N ratios of 4 to 30 which is 1 to 2 orders of magnitude higher compared to modern corals. Al concentrations are low (<10 ppm) and do not correlate with REE concentrations indicating an insignificant fraction of terrigenous material included in the skeleton. Applying distribution coefficients typical for modern corals, the REE composition of the Tortonian ambient water yields (La/Lu)N of about 2 to 16. This range can be explained by binary mixing of modern Eastern Mediterranean sea surface water ((La/Lu)N=0.35, sea surface salinity (SSS) ~38 ‰) with highly LREE-enriched river water ((La/Lu)N >3, salinity ~0.5 ‰) transporting suspended and colloid phases, also highly enriched, especially in LREE, at a ratio of ~9 (seawater):1 (river water). The river water component is considered because paleoenvironmental

  16. Anthropogenic disturbance of element cycles at the Earth's surface.

    PubMed

    Sen, Indra S; Peucker-Ehrenbrink, Bernhard

    2012-08-21

    The extent to which humans are modifying Earth's surface chemistry can be quantified by comparing total anthropogenic element fluxes with their natural counterparts (Klee and Graedel, 2004). We quantify anthropogenic mass transfer of 77 elements from mining, fossil fuel burning, biomass burning, construction activities, and human apportionment of terrestrial net primary productivity, and compare it to natural mass transfer from terrestrial and marine net primary productivity, riverine dissolved and suspended matter fluxes to the ocean, soil erosion, eolian dust, sea-salt spray, cosmic dust, volcanic emissions, and for helium, hydrodynamic escape from the Earth's atmosphere. We introduce an approach to correct for losses during industrial processing of elements belonging to geochemically coherent groups, and explicitly incorporate uncertainties of element mass fluxes through Monte Carlo simulations. We find that at the Earth's surface anthropogenic fluxes of iridium, osmium, helium, gold, ruthenium, antimony, platinum, palladium, rhenium, rhodium and chromium currently exceed natural fluxes. For these elements mining is the major factor of anthropogenic influence, whereas petroleum burning strongly influences the surficial cycle of rhenium. Our assessment indicates that if anthropogenic contributions to soil erosion and eolian dust are considered, anthropogenic fluxes of up to 62 elements surpass their corresponding natural fluxes. PMID:22803636

  17. Multi-objective optimization of chromatographic rare earth element separation.

    PubMed

    Knutson, Hans-Kristian; Holmqvist, Anders; Nilsson, Bernt

    2015-10-16

    The importance of rare earth elements in modern technological industry grows, and as a result the interest for developing separation processes increases. This work is a part of developing chromatography as a rare earth element processing method. Process optimization is an important step in process development, and there are several competing objectives that need to be considered in a chromatographic separation process. Most studies are limited to evaluating the two competing objectives productivity and yield, and studies of scenarios with tri-objective optimizations are scarce. Tri-objective optimizations are much needed when evaluating the chromatographic separation of rare earth elements due to the importance of product pool concentration along with productivity and yield as process objectives. In this work, a multi-objective optimization strategy considering productivity, yield and pool concentration is proposed. This was carried out in the frame of a model based optimization study on a batch chromatography separation of the rare earth elements samarium, europium and gadolinium. The findings from the multi-objective optimization were used to provide with a general strategy for achieving desirable operation points, resulting in a productivity ranging between 0.61 and 0.75 kgEu/mcolumn(3), h(-1) and a pool concentration between 0.52 and 0.79 kgEu/m(3), while maintaining a purity above 99% and never falling below an 80% yield for the main target component europium. PMID:26375205

  18. Dissolved Rare Earth Element Concentrations in the Upwelling area off Peru

    NASA Astrophysics Data System (ADS)

    Grasse, P.; Plass, A.; Hathorne, E. C.; Frank, M.

    2012-12-01

    Rare earth elements (REEs) are powerful tracers of continental input, particle exchange and scavenging processes, as well as for water mass transport in the ocean. We present a first data set of dissolved REE distributions in filtered seawater covering the major gradients of bio-productivity and oxygen concentrations in the upwelling area off Peru. A total of 22 stations were analyzed along a shelf, a nearshore and an offshore transect to investigate the influence of local inputs versus water mass mixing. The Peruvian coastal upwelling area is a highly dynamic system characterized by intense upwelling of nutrient-rich subsurface water and therefore high productivity that leads to one of the globally largest Oxygen Minimum Zones (OMZ). The upwelling area off Peru is of particular interest for understanding the biogeochemical cycling of REEs and other redox-sensitive metals because anoxic conditions are expected to release of REEs from the shelf, whereas high particle densities and fluxes efficiently remove the REEs from the water column. Despite their high potential as tracers few systematic investigations of seawater REEs have been carried out so far because the low concentrations of REEs (pM) are difficult to measure. In this study an online preconcentration (OP) system (seaFast, Elemental Scientific Inc.) was used with a technique slightly modified from Hathorne et al. (2012). The OP system efficiently separates seawater matrix elements from the REEs and elutes the preconcentrated sample directly into the spray chamber of the ICP-MS instrument. Repeated measurements of a seawater reference sample (n= 20) during this study gave a reproducibility of between 5% and 15% (2σ), with the worst reproducibility for Sm, Eu, and Gd (12% to 15%). In general, the REEs, except Ce, show a nutrient-like behavior in seawater increasing in concentration with water depth. However, such distributions were not observed for some stations on the shelf where the highest concentrations

  19. An EDTA-β-cyclodextrin material for the adsorption of rare earth elements and its application in preconcentration of rare earth elements in seawater.

    PubMed

    Zhao, Feiping; Repo, Eveliina; Meng, Yong; Wang, Xueting; Yin, Dulin; Sillanpää, Mika

    2016-03-01

    The separation and recovery of Rare earth elements (REEs) from diluted aqueous streams has attracted great attention in recent years because of ever-increasing REEs demand. In this study, a green synthesized EDTA-cross-linked β-cyclodextrin (EDTA-β-CD) biopolymer was prepared and employed in adsorption of aqueous REEs, such as La(III), Ce(III), and Eu(III). EDTA acts not only as cross-linker but also as coordination site for binding of REEs. The adsorption properties for the adsorption of REEs by varying experimental conditions were carried out by batch tests. The kinetics results revealed that the surface chemical sorption and the external film diffusion were the rate-determining steps of the adsorption process. The obtained maximum adsorption capacities of EDTA-β-CD were 0.343, 0.353, and 0.365mmolg(-1) for La(III), Ce(III) and Eu(III), respectively. Importantly, the isotherms fitted better to Langmuir than Freundlich and Sips models, suggesting a homogenous adsorption surface for REEs on the adsorbent. Moreover, the multi-component adsorption, which was modeled by extended Sips isotherms, revealed adsorbent's selectivity to Eu(III). More significantly, the successful recoveries of the studied ions from tap water and seawater samples makes EDTA-β-CD a promising sorbent for the preconcentration of REEs from diluted aqueous streams. PMID:26674238

  20. Experimental constraints on light elements in the Earth's outer core.

    PubMed

    Zhang, Youjun; Sekine, Toshimori; He, Hongliang; Yu, Yin; Liu, Fusheng; Zhang, Mingjian

    2016-01-01

    Earth's outer core is liquid and dominantly composed of iron and nickel (~5-10 wt%). Its density, however, is ~8% lower than that of liquid iron, and requires the presence of a significant amount of light element(s). A good way to specify the light element(s) is a direct comparison of density and sound velocity measurements between seismological data and those of possible candidate compositions at the core conditions. We report the sound velocity measurements of a model core composition in the Fe-Ni-Si system at the outer core conditions by shock-wave experiments. Combining with the previous studies, we found that the best estimate for the outer core's light elements is ~6 wt% Si, ~2 wt% S, and possible ~1-2.5 wt% O. This composition satisfies the requirements imposed by seismology, geochemistry, and some models of the early core formation. This finding may help us to further constrain the thermal structure of the Earth and the models of Earth's core formation. PMID:26932596

  1. Post-depositional redistribution processes and their effects on middle rare earth element precipitation and the cerium anomaly in sediments in the South Korea Plateau, East Sea

    NASA Astrophysics Data System (ADS)

    Kang, Jeongwon; Jeong, Kap-Sik; Cho, Jin Hyung; Lee, Jun Ho; Jang, Seok; Kim, Seong Ryul

    2014-03-01

    We sampled two box-core sediments from the slope of the eastern South Korea Plateau (SKP) in the East Sea (Sea of Japan) at water depths of 1400 and 1700 m. Two chemical fractions of extractable (hydroxylamine/acetic acid) and residual rare earth elements (REEs) together with Al, Ca, Fe, Mg, Mn, P, S, As, Mo, and U were analyzed to assess the post-depositional redistribution of REEs. Extractable Fe and Mn are noticeably abundant in the oxic topmost sediment layer (<3 cm). However, some trace elements (e.g., S, As, Mo, U) are more abundant at depth, where redox conditions are different. Analysis of upper continental crust (UCC)-normalized (La/Gd)UCC, (La/Yb)UCC, and (Ce/Ce*)UCC revealed that the extractable REE is characterized by middle REE (MREE) enrichment and a positive cerium (Ce) anomaly, different from the case of the residual fraction which shows slight enrichment in light REEs (LREEs) with no Ce anomaly. The extractable MREEs seem to have been incorporated into high-Mg calcite during reductive dissolution of Fe oxyhydroxides. In the top sediment layer, the positive Ce anomaly is attributed to Ce oxide, which can be mobilized in deeper oxygen-poor environments and redistributed in the sediment column. In addition, differential concentrations of Ce and other LREEs in pore water appear to result in variable (Ce/Ce*)UCC ratios in the extractable fraction at depth.

  2. Chemical properties of rare earth elements in typical medical waste incinerator ashes in China.

    PubMed

    Zhao, Lijuan; Zhang, Fu-Shen; Zhang, Jingxin

    2008-10-30

    Medical waste (MW) ashes from different types of MW incinerators were examined to detect the characteristics and environmental impact of rare earth elements (REEs). The results showed that total REE contents in the ash samples ranged from 10.2 to 78.9 mg/kg. REEs in bottom ash were apparently higher than those in fly ash. Average REE contents in the ashes followed the sequence of Ce>La>Nd>Y>Gd>Pr>Sm>Dy>Er>Yb>Ho>Eu>Tb>Lu>Tm. Some of the elements, such as Sm, Dy, Ho, Er, Yb in the ash samples were in normal or nearly normal distribution, but Y, La, Ce, Pr, Nd, Eu, Gd, Tb, Tm, Lu were not normally distributed, indicating some of the ash samples were enriched with these elements. Crust-normalized REE patterns indicated that two types of the MW ashes were obviously enriched with Gd and La. Sequential extraction results showed that REEs in the ash mainly presented as residual fraction, while exchangeable and carbonate fractions were relatively low. DTPA- and EDTA-extraction tests indicated that REEs in the MW ashes were generally in low bioavailability. PMID:18329796

  3. Coal fly ash as a resource for rare earth elements.

    PubMed

    Franus, Wojciech; Wiatros-Motyka, Małgorzata M; Wdowin, Magdalena

    2015-06-01

    Rare earth elements (REE) have been recognised as critical raw materials, crucial for many clean technologies. As the gap between their global demand and supply increases, the search for their alternative resources becomes more and more important, especially for the countries which depend highly on their import. Coal fly ash (CFA), which when not utilised is considered waste, has been regarded as the possible source of many elements, including REE. Due to the increase in the energy demand, CFA production is expected to grow, making research into the use of this material a necessity. As Poland is the second biggest coal consumer in the European Union, the authors have studied different coal fly ashes from ten Polish power plants for their rare earth element content. All the fly ashes have a broadly similar distribution of rear earth elements, with light REE being dominant. Most of the samples have REE content relatively high and according to Seredin and Dai (Int J Coal Geol 94: 67-93, 2012) classification can be considered promising REE raw materials. PMID:25613802

  4. Rare-earth elements in Egyptian granite by instrumental neutron activation analysis.

    PubMed

    El-Taher, A

    2007-04-01

    The mobilization of rare-earth elements (REEs) in the environment requires monitoring of these elements in environmental matrices, in which they are mainly present at trace levels. The similarity in REEs chemical behavior makes the separate determination of each element by chemical methods difficult; instrumental neutron activation analysis (INAA), based on nuclear properties of the elements to be determined, is a method of choice in trace analysis of REEs and related elements. Therefore, INAA was applied as a sensitive nondestructive analytical tool for the determination of REEs to find out what information could be obtained about the REEs of some Egyptian granite collected from four locations in Aswan area in south Egypt as follows wadi El-Allaqi, El-Shelal, Gabel Ibrahim Pasha and from Sehyel Island and to estimate the accuracy, reproducibility and detection limit of NAA method in case of the given samples. The samples were properly prepared together with standards and simultaneously irradiated in a neutron flux of 7 x 10(11)n/cm(2)s in the TRIGA Mainz research reactor facilities. The following elements have been determined: La, Ce, Nd, Sm, Eu, Yb and Lu. The gamma spectra was collected by HPGe detector and the analysis was done by means of computerized multichannel analyzer. The X-ray fluorescence (XRF) was also used. PMID:17208446

  5. Geochemical fractions of rare earth elements in soil around a mine tailing in Baotou, China

    NASA Astrophysics Data System (ADS)

    Wang, Lingqing; Liang, Tao

    2015-07-01

    Rare earth mine tailing dumps are environmental hazards because tailing easily leaches and erodes by water and wind. To assess the influence of mine tailing on the geochemical behavior of rare earth elements (REEs) in soil, sixty-seven surface soil samples and three soil profile samples were collected from different locations near China’s largest rare earth mine tailing. The total concentration of REEs in surface soils ranged from 156 to 5.65 × 104 mg·kg-1 with an average value of 4.67 × 103 mg·kg-1, which was significantly higher than the average value in China (181 mg·kg-1). We found obvious fractionation of both light and heavy REEs, which was supported by the North American Shale Composite (NASC) and the Post-Archean Average Australian Shale (PAAS) normalized concentration ratios calculated for selected elements (LaN/YbN, LaN/SmN and GdN/YbN). A slightly positive Ce anomaly and a negative Eu anomaly were also found. For all 14 REEs in soils, enrichment was intensified by the mine tailing sources and influenced by the prevailing wind.

  6. Geochemical fractions of rare earth elements in soil around a mine tailing in Baotou, China.

    PubMed

    Wang, Lingqing; Liang, Tao

    2015-01-01

    Rare earth mine tailing dumps are environmental hazards because tailing easily leaches and erodes by water and wind. To assess the influence of mine tailing on the geochemical behavior of rare earth elements (REEs) in soil, sixty-seven surface soil samples and three soil profile samples were collected from different locations near China's largest rare earth mine tailing. The total concentration of REEs in surface soils ranged from 156 to 5.65 × 10(4) mg·kg(-1) with an average value of 4.67 × 10(3) mg·kg(-1), which was significantly higher than the average value in China (181 mg·kg(-1)). We found obvious fractionation of both light and heavy REEs, which was supported by the North American Shale Composite (NASC) and the Post-Archean Average Australian Shale (PAAS) normalized concentration ratios calculated for selected elements (La(N)/Yb(N), La(N)/Sm(N) and Gd(N)/Yb(N)). A slightly positive Ce anomaly and a negative Eu anomaly were also found. For all 14 REEs in soils, enrichment was intensified by the mine tailing sources and influenced by the prevailing wind. PMID:26198417

  7. Geochemical fractions of rare earth elements in soil around a mine tailing in Baotou, China

    PubMed Central

    Wang, Lingqing; Liang, Tao

    2015-01-01

    Rare earth mine tailing dumps are environmental hazards because tailing easily leaches and erodes by water and wind. To assess the influence of mine tailing on the geochemical behavior of rare earth elements (REEs) in soil, sixty-seven surface soil samples and three soil profile samples were collected from different locations near China’s largest rare earth mine tailing. The total concentration of REEs in surface soils ranged from 156 to 5.65 × 104 mg·kg−1 with an average value of 4.67 × 103 mg·kg−1, which was significantly higher than the average value in China (181 mg·kg−1). We found obvious fractionation of both light and heavy REEs, which was supported by the North American Shale Composite (NASC) and the Post-Archean Average Australian Shale (PAAS) normalized concentration ratios calculated for selected elements (LaN/YbN, LaN/SmN and GdN/YbN). A slightly positive Ce anomaly and a negative Eu anomaly were also found. For all 14 REEs in soils, enrichment was intensified by the mine tailing sources and influenced by the prevailing wind. PMID:26198417

  8. Contamination in the Rare-Earth Element Orthophosphate Reference Samples

    PubMed Central

    Donovan, John J.; Hanchar, John M.; Picolli, Phillip M.; Schrier, Marc D.; Boatner, Lynn A.; Jarosewich, Eugene

    2002-01-01

    Several of the fourteen rare-earth element (plus Sc and Y) orthophosphate standards grown at Oak Ridge National Laboratory in the 1980s and widely distributed by the Smithsonian Institution’s Department of Mineral Sciences, are significantly contaminated by Pb. The origin of this impurity is the Pb2P2O7 flux that is derived from the thermal decomposition of PbHPO4. The lead pyrophosphate flux is used to dissolve the oxide starting materials at elevated temperatures (≈1360 °C) prior to the crystal synthesis. Because these rare-earth element standards are extremely stable under the electron beam and considered homogenous, they have been of enormous value to electron probe micro-analysis (EPMA). The monoclinic, monazite structure, orthophosphates show a higher degree of Pb incorporation than the tetragonal xenotime structure, orthophosphates. This paper will attempt to describe and rationalize the extent of the Pb contamination in these otherwise excellent materials.

  9. Rare earth element content in various waste ashes and the potential risk to Japanese soils.

    PubMed

    Zhang, F S; Yamasaki, S; Kimura, K

    2001-11-01

    Selected chemical characteristics of rare earth elements (REEs) in 89 waste ash samples, including food scrap ashes (FSA), animal waste ashes (AWA), horticulture waste ashes (HWA), sewage sludge ashes (SSA) and incinerator bottom ashes (IBA), were examined in this study. The results showed that Y, La, Ce, Pr, Nd, Dy, Yb, Ho, Er, Tm, Lu in the waste ash samples were normally distributed, but Sc, Sm, Eu, Gd, Tb were not. Average REE concentrations followed the sequence of Ce > La = Y> Sc>Nd>Sm>Pr>Gd>Dy>Eu>Tb>Er> Yb>Ho>Lu>Tm. Of the five types of waste ashes, total REE contents (sigmaREE) ranged from 54 to 130 mg/kg, following the sequence of SSA>HWA>IBA>AWA>FSA; individual REE concentrations were within 0.04-20, 0.1-29, 0.2-33, 0.1-44 and 0.01-41 mg/kg for FSA, AWA, HWA, SSA and IBA, respectively. Crust-normalized REE patterns indicated that SSA was enriched with Sc, Sm, Eu, Gd, Tb and slightly enriched with La, Ce; IBA was enriched with Eu, Tb and slightly with La, Y, Ce; FSA was slightly enriched with Sm, Eu, Tb; REEs were not found to be elevated in HWA and AWA. Comparison of REE content in the waste ashes and in six principal Japanese agricultural soils indicated that application of FSA, AWA and HWA to agricultural land will cause no REE problem, but continuous application of SSA or IBA may cause Sc, Sm or Eu accumulation in some of the soils. PMID:11757853

  10. Determination of the Earth's plasmapause location from the CE-3 EUVC images

    NASA Astrophysics Data System (ADS)

    He, Fei; Zhang, Xiao-Xin; Chen, Bo; Fok, Mei-Ching; Nakano, Shinya

    2016-01-01

    The Moon-based Extreme Ultraviolet Camera (EUVC) aboard China's Chang'e-3 (CE-3) mission has successfully imaged the entire Earth's plasmasphere for the first time from the side views on lunar surface. An EUVC image on 21 April 2014 is used in this study to demonstrate the characteristics and configurations of the Moon-based EUV imaging and to illustrate the determination algorithm of the plasmapause locations on the magnetic equator. The plasmapause locations determined from all the available EUVC images with the Minimum L Algorithm are quantitatively compared with those extracted from in situ observations (Defense Meteorological Satellite Program, Time History of Events and Macroscale Interactions during Substorms, and Radiation Belt Storm Probes). Excellent agreement between the determined plasmapauses seen by EUVC and the extracted ones from other satellites indicates the reliability of the Moon-based EUVC images as well as the determination algorithm. This preliminary study provides an important basis for future investigation of the dynamics of the plasmasphere with the Moon-based EUVC imaging.

  11. Trace and rare earth elemental variation in Arabian sea sediments through a transect across the oxygen minimum zone

    SciTech Connect

    Nath, B.N.; Rao, B.R.; Rao, C.M.; Bau, M.

    1997-06-01

    We have determined the calcium carbonate (CaCO{sub 3}), organic carbon (C{sub org}), trace element, and rare earth element (REE) composition of surface sediments collected from a transect on the central western continental shelf and slope of India in the Eastern Arabian Sea. The transect samples across the oxygen minimum zone (OMZ) allows us to compare the relative abundances of trace elements and REEs in the sediments beneath and beyond the OMZ. Shale-normalized REE patterns, La{sub n}/Yb{sub n} ratios, and Eu/Eu* anamolies indicate that the sediments in the study area are either derived from the adjoining Archaean land masses or from distal Indus source. Sediment deposited in the OMZ have high U values from 3.6 to 8.1 ppm, with their U{sub excess} (of that can be supplied by continental particles) values ranging between 82-91% of the total U, indicating that the U may be precipitated as U{sup +4} in the reducing conditions of OMZ. Sediments deposited beneath the intense OMZ (<0.2 mL/L) and away from the OMZ (1-2 mL/L) show slight negative Ce anomalies, with no significant differences between these two sets of sediments. The Ce/Ce*{sub shale} values are poorly related to U and C{sub org} which are indicators of suboxic bottom waters. Normative calculations suggest that two sources, namely, terrestrial and seawater (terrestrial > seawater) contribute to the total Ce anomaly of the sediments. The Ce anomaly values of the calculated seawater derived component are similar to the anomalies reported for other coastal waters and the oxygenated surface waters of the Arabian Sea and do not show any correspondence to the lowered redox state of the overlying water, probably due to the redirection of dissolved Ce into the oxic deeper water. 103 refs., 6 figs., 3 tabs.

  12. Dissolved rare earth elements in the South China Sea: Geochemical characterization of the water masses

    NASA Astrophysics Data System (ADS)

    Alibo, Dia Sotto; Nozaki, Yoshiyuki

    2000-12-01

    We have measured the vertical profiles of dissolved rare earth elements (REEs) and yttrium in the South China Sea together with conductivity-temperature-depth and hydrographic measurements to compare with those in the western North Pacific and the SuIu Sea. Although the South China Sea is rapidly flushed by the Pacific through the Luzon Strait with a sill depth of ˜2500 m [Broecker et al., 1986], a unique REE pattern is developed within the sea. The most striking difference exists in the dissolved Ce profiles. Dissolved Ce generally decreases from high values (6-9 pmol/kg) at the surface to a minimum of ˜3 pmol/kg at around 300-500 m where the North Pacific Intermediate Water penetrates. In deepwaters of the North Pacific and the Sulu Sea it remains at a relatively low and nearly constant concentration level of ˜5 pmol/kg throughout the water column, whereas in the South China Sea, it gradually increases with depth to a maximum of 12.9 pmol/kg at ˜2500 m, resembling the "nutrient-like" profiles of other strictly trivalent REEs, and then sharply drops to a constant value of ˜6 pmol/kg in the bottom water below 2900 m. Some lighter REEs like Pr, Nd, and Gd, though to a much lesser extent, also show similar concentration breaks at the sill depth, but the other hydrographic properties like dissolved oxygen, nutrients, pH, and alkalinity do not. Therefore dissolved REEs may best be utilized to characterize the water masses. Two major sources for dissolved REEs in the South China Sea are fluvial and coastal input to the surface ocean and a bottom release into the deep water during the passage over the Luzon Strait. Redox chemistry including reduction of Ce(IV) to Ce(III) in the pore water of hemipelagic sediments and subsequent release of dissolved Ce(III) to the overlying deep water may be involved in the latter. The middle REE-enriched patterns with a significant Gd depression relative to that of the North Pacific Deep Water are characteristic of the South China

  13. Rare Earth Element Fractionation During Evaporation of Chondritic Material

    NASA Astrophysics Data System (ADS)

    Wang, J.; Davis, A. M.; Clayton, R. N.

    1993-07-01

    Evaporation experiments suggest that enrichments in the heavy isotopes of oxygen, magnesium, and silicon in some CAIs are caused by kinetic effects during evaporation [1]. Volatility-fractionated REE patterns found in some CAIs have been modeled with some success using equilibrium thermodynamics [2,3], but little is known about kinetic effects on REE patterns. We have begun an investigation of REE fractionation under conditions where large isotope effects are produced by the kinetic isotope effect. We synthesized a starting material containing CI chondritic relative proportions of MgO, Al2O3, SiO2, CaO, TiO2, and FeO, and doped it with 100 ppm each of the REE. Samples of this material were evaporated in a vacuum furnace [4] at 10^-6 torr and 1800 or 2000 degrees C for periods of a few seconds to 5 hr. The mass fraction evaporated ranged from 7.6 to 95.4%. Most residues consist of olivine and glass. Chemical compositions of the residues were determined by electron and ion microprobe. Results for selected elements are shown in Fig. 1. There is no significant evaporation of Ca, Al, and Ti up to 95% mass loss; the evaporation behavior of Mg, Si, and Fe is similar to that found by Hashimoto [5]. There is no significant evaporation of most of the REE up to 95% mass loss. Ce is much more volatile than the other REE under these conditions: a tenfold negative Ce anomaly developed between 60 and 70% mass loss and the anomaly reached 5 X 10^-4 at 95% mass loss. A small Pr anomaly (50% Pr loss) also appeared in the highest-mass-loss residue. Thermodynamic calculations show that Ce has approximately the same volatility as other LREE under solar nebular oxygen fugacity, but is much more volatile than the other REE under oxidizing conditions [6]. We suspect that conditions in the residue in our vacuum evaporation experiments became oxidizing because evaporation reactions involving most major element oxides involve release of oxygen. The four known HAL-type hibonite

  14. Anthropogenic rare earth element fluxes into floodplains: Coupling between geochemical monitoring and hydrodynamic sediment transport modelling

    NASA Astrophysics Data System (ADS)

    Hissler, Christophe; Hostache, Renaud; Iffly, Jean François; Pfister, Laurent; Stille, Peter

    2015-09-01

    As all rare earth elements (REEs) have an increasingly important role in high tech industries, they are now recognized as emergent pollutants in river systems impacted by anthropogenic activity. Over the past 20 years, significant anthropogenic contributions were reported for Gd, La and Sm, and we may expect that REE contamination in rivers is to further increase in a near future. Despite the work done to assess the environmental impact of REE pollutions in larger river systems, we are still lacking information on the dynamics of these anthropogenic compounds in relation to hydrological changes. Here, we observed for the first time particulate Ce originating from local industrial activities in Luxembourg and we quantified the anthropogenic contribution to the REE fluxes at the river basin scale during a single flood event.

  15. The distribution of Sr and REE between diopside and silicate liquid. [Rare Earth Elements

    NASA Technical Reports Server (NTRS)

    Grutzeck, M.; Kridelbaugh, S.; Weill, D.

    1974-01-01

    Experimental determination of the distribution coefficients in diopside-liquid pairs for strontium and nine rare-earth elements in the system CaMgSi2O6-NaAlSi3O8-CaAl2Si2O8. In experiments in air at 1265 C it is found that most of the Sr(2+), Eu(2+), and RE(3+) ions substitute for Ca(2+) and, in addition, a coupled substitution of Al(3+) for Si(4+) occurs. All of the trace ions considered are found to be excluded from the diopside lattice relative to the liquid. In the case of the trivalent ions the exclusion is much more pronounced for La and Ce, which have ionic radii larger than that of Ca(2+) in 8-fold oxygen coordination. Divalent Sr and Eu with even larger radii are also strongly excluded.

  16. Rare earth and trace element geochemistry of a fragment of Jurassic seafloor, Point Sal, California

    NASA Technical Reports Server (NTRS)

    Menzies, M.; Blanchard, D.; Brannon, J.; Korotev, R.

    1977-01-01

    Rocks from an ophiolite suite once on the seafloor were analyzed for rare earth elements (REE), Sc, Co, Na2O, Cr, Zn and FeO. Strontium isotope exchange noted in some of the lavas is attributed to basalt-seawater interaction; the Ce abundance in smectite- and zeolite-bearing lavas may also be due to prolonged exposure to seawater. The higher grades of metamorphic rock, however, show no variation from the usual flat or slightly light REE depleted profiles. Plutonic igneous rock, all light REE depleted, have total REE abundances varying by a factor of 100 between the dunites and diorites. In order of decreasing REE abundance are hornblende, clinopyroxene, plagioclase, orthopyroxene and olivine. Calculations of REE contents of liquids in equilibrium with early cumulative clinopyroxenes suggest that the parent to the stratiform sequence was more depleted in light REE than the parent to the lava pile.

  17. Geochemistry of rare earth elements in a passive treatment system built for acid mine drainage remediation.

    PubMed

    Prudêncio, Maria Isabel; Valente, Teresa; Marques, Rosa; Sequeira Braga, Maria Amália; Pamplona, Jorge

    2015-11-01

    Rare earth elements (REE) were used to assess attenuation processes in a passive system for acid mine drainage treatment (Jales, Portugal). Hydrochemical parameters and REE contents in water, soils and sediments were obtained along the treatment system, after summer and winter. A decrease of REE contents in the water resulting from the interaction with limestone after summer occurs; in the wetlands REE are significantly released by the soil particles to the water. After winter, a higher water dynamics favors the AMD treatment effectiveness and performance since REE contents decrease along the system; La and Ce are preferentially sequestered by ochre sludge but released to the water in the wetlands, influencing the REE pattern of the creek water. Thus, REE fractionation occurs in the passive treatment systems and can be used as tracer to follow up and understand the geochemical processes that promote the remediation of AMD. PMID:26247412

  18. Anthropogenic Disturbance of Element Cycles at the Earth's Surface

    NASA Astrophysics Data System (ADS)

    Sen, I. S.; Peucker-Ehrenbrink, B.

    2012-12-01

    The extent to which humans are modifying Earth's surface chemistry can be quantified by comparing total anthropogenic element fluxes with their natural counterparts [1]. We determine anthropogenic mass transfer of 77 elements from mining, fossil fuel burning, biomass burning, construction activities, and human apportionment of terrestrial net primary productivity, and compared it to natural mass transfer from terrestrial and marine net primary productivity, riverine dissolved and suspended matter fluxes to the ocean, soil erosion, eolian dust, sea-salt spray, cosmic dust, volcanic emissions and - for helium - hydrodynamic escape from the Earth's atmosphere. In addition, we introduce an approach to correct for losses during industrial processing of elements belonging to geochemically coherent groups, and explicitly incorporated uncertainties of element mass fluxes through Monte Carlo simulations [2]. Our assessment indicates that anthropogenic fluxes of iridium, osmium, helium, gold, ruthenium, antimony, platinum, palladium, rhenium, rhodium and chromium are greater than the respective natural fluxes. For these elements mining is the major factor of human dominance, whereas petroleum burning strongly influence the surficial cycle of rhenium. Apart from these 11 elements there are 15 additional elements whose anthropogenic fluxes may surpass their corresponding natural fluxes. Anthropogenic fluxes of the remaining elements are smaller than their corresponding natural fluxes although a significant human influence is observed for all of them. For example, ~20% of the annual fluxes of C, N, and P can be attributed to human activities. Such disturbances, though small compared with natural fluxes, can significantly alter concentrations in near-surface reservoirs and affect ecosystems if they are sustained over time scales similar to or longer than the residence time of elements in the respective reservoir. Examples are the continuing input of CO2 to the atmosphere that

  19. X-ray fluorescence analysis of rare earth elements in rocks using low dilution glass beads.

    PubMed

    Nakayama, Kenichi; Nakamura, Toshihiro

    2005-07-01

    Major and trace elements (Na, Mg, Al, Si, P, K, Ca, Ti, Mn, Fe, Rb, Sr, Y, Zr, La, Ce, Pr, Nd, Sm, Gd, Dy, Th and U) in igneous rocks were assayed with fused lithium borate glass beads using X-ray fluorescence spectrometry. Low dilution glass beads, which had a 1:1 sample-to-flux ratio, were prepared for determination of rare earth elements. Complete vitrification of 1:1 mixture required heating twice at 1200 degrees C with agitation. Extra pure reagents containing determinants were used for calibrating standards instead of the rock standard. The calibration curves of the 23 elements showed good linearity. Furthermore, the lower limits of detection corresponding to three times the standard deviation for blank measurements were 26 mass ppm for Na2O, 6.7 for MgO, 4.5 for Al2O3, 4.5 for SiO2, 18 for P2O5, 1.1 for K2O, 4.0 for CaO, 3.9 for TiO2, 1.6 for MnO, 0.8 for Fe2O3, 0.5 for Rb, 0.2 for Sr, 0.4 for Y, 0.5 for Zr, 3.3 for La, 6.5 for Ce, 2.7 for Pr, 2.1 for Nd, 1.7 for Sm, 0.7 for Gd, 2.7 for Dy, 0.5 for Th, and 0.6 for U. Using the present method, we determined the contents of these 23 elements in four rhyolitic and granitic rocks from Japan. PMID:16038502

  20. Sensitized red luminescence from Ce{sup 3+}, Mn{sup 2+}-doped glaserite-type alkaline-earth silicates

    SciTech Connect

    Yonesaki, Yoshinori; Takei, Takahiro; Kumada, Nobuhiro; Kinomura, Nobukazu

    2010-06-15

    Bright red luminescence is observed from Ce, Mn-doped glaserite-type alkaline-earth silicates with M{sub 2}BaMgSi{sub 2}O{sub 8} (M: Ba, Sr, Ca) chemical composition. Under UV excitation, Ce-doped M{sub 2}BaMgSi{sub 2}O{sub 8} exhibits strong near-UV emission with asymmetric peak shape. UV-excited Mn-doped M{sub 2}BaMgSi{sub 2}O{sub 8} compounds show visible red emission only when Ce{sup 3+} ions are doped together. These results indicate that Mn{sup 2+}-derived red emission is caused by an efficient energy transfer from Ce{sup 3+} to Mn{sup 2+}. The red emission becomes intense with an increase in Ba-amount. This trend originates from the relaxation of the selection rule for 3d-3d transition in Mn{sup 2+} ions, which is caused by the structural deformation due to Ba{sup 2+} occupation for layer-pockets. - Graphical abstract: Glaserite-type red emitting phosphor, M{sub 2}BaMgSi{sub 2}O{sub 8}: Ce{sup 3+}, Mn{sup 2+} (M: Ba, Sr, Ca), was prepared by solid state reaction. Under UV excitation, Mn{sup 2+}-derived red emission is observed from the compounds only when Ce{sup 3+} ions are codoped, indicating that the red emission is caused by an energy transfer from Ce{sup 3+} to Mn{sup 2+}.

  1. The Earth Based Ground Stations Element of the Lunar Program

    NASA Technical Reports Server (NTRS)

    Gal-Edd, Jonathan; Fatig, Curtis; Schier, James; Lee, Charles

    2007-01-01

    The Lunar Architecture Team (LAT) is responsible for developing a concept for building and supporting a lunar outpost with several exploration capabilities such as rovers, colonization, and observatories. The lunar outpost is planned to be located at the Moon's South Pole. The LAT Communications and Navigation Team (C&N) is responsible for defining the network infrastructure to support the lunar outpost. The following elements are needed to support lunar outpost activities: A Lunar surface network based on industry standard wireless 802.xx protocols, relay satellites positioned 180 degrees apart to provide South Pole coverage for the half of the lunar 28-day orbit that is obscured from Earth view, earth-based ground stations deployed at geographical locations 120 degrees apart. This paper will focus on the Earth ground stations of the lunar architecture. Two types of ground station networks are discussed. One provides Direct to Earth (DTE) support to lunar users using Kaband 23/26Giga-Hertz (GHz) communication frequencies. The second supports the Lunar Relay Satellite (LRS) that will be using Ka-band 40/37GHz (Q-band). This paper will discuss strategies to provide a robust operational network in support of various lunar missions and trades of building new antennas at non-NASA facilities, to improve coverage and provide site diversification for handling rain attenuation.

  2. The application of GNSS in the near-Earth navigation of China’s lunar probe CE-5T1

    NASA Astrophysics Data System (ADS)

    Huang, Yong; Fan, Min; Hu, Xiaogong; Li, Peijia

    2015-08-01

    After CE-1, CE-2 and CE-3, China’s fourth lunar probe CE-5T1 was launched on 23 Oct., 2014, which goal is to test the returning capability of the lunar probe. On 31 Oct., the landing portion of CE-5T1 successfully landed in the North China. CE-5T1 is a high eccentricity orbit with apogee of about 413 thousand km. A GNSS receiver was installed in CE-5T1 to test the ability of GNSS navigation for a High Earth Orbit (HEO) spacecraft. The receiver performed well and GPS side lobe signals have been tracked when the probe was at an altitude from 10000 to 60000 km during about two 3-hours periods, and most of time it is above the altitude of the GPS constellation. In these two periods, the average GPS satellites tracked is about 8-9, and the GDOP is from 1 to 30. We processed these GNSS data after the mission, and the noise level of the differenced pseudo-range is less than 10 m. We used the GNSS data to determine the orbit of CE-5T1, compared with the use of ground based tracking data including range, Doppler and VLBI. The results are encouraging, and the position difference between orbit determination (OD) with GNSS data and ground based data is less than 100 m. In CE-5T1 mission, the separation point is about 5000 km altitude, where the lander will separate from the orbiter then return to the ground. The separation point prediction accuracy directly affects the landing position. As plan there is a maneuver about 5 hours before the separation (canceled in fact), so there is only 3-4 hours tracking data to be used to predict the separation point. Analysis shows that combination of two types of data can improve the orbit accuracy as well as the accuracy of the predicted orbit. CE-5T1 made a successful test of the GNSS using for HEO spacecraft. Obviously, GNSS can be used as a low-cost OD sensor and the use of GNSS technique can reduce the observing pressure of the ground antenna in the lunar and deep space exploration.

  3. Rare earth elements in the water column of Lake Vanda, McMurdo Dry Valleys, Antarctica

    NASA Astrophysics Data System (ADS)

    De Carlo, Eric Heinen; Green, William J.

    2002-04-01

    We present data on the composition of water from Lake Vanda, Antarctica. Vanda and other lakes in the McMurdo Dry Valleys of Antarctica are characterized by closed basins, permanent ice covers, and deep saline waters. The meromictic lakes provide model systems for the study of trace metal cycling owing to their pristine nature and the relative simplicity of their biogeochemical systems. Lake Vanda, in the Wright Valley, is supplied by a single input, the Onyx River, and has no output. Water input to the lake is balanced by sublimation of the nearly permanent ice cap that is broken only near the shoreline during the austral summer. The water column is characterized by an inverse thermal stratification of anoxic warm hypersaline water underlying cold oxic freshwater. Water collected under trace-element clean conditions was analyzed for its dissolved and total rare earth element (REE) concentrations by inductively coupled plasma mass spectrometry. Depth profiles are characterized by low dissolved REE concentrations (La, Ce, <15 pM) in surface waters that increase slightly (La, 70 pM; Ce, 20 pM) with increasing depth to ˜55 m, the limit of the fresh oxic waters. Below this depth, a sharp increase in the concentrations of strictly trivalent REE (e.g., La, 5 nM) is observed, and a submaximum in redox sensitive Ce (2.6 nM) is found at 60- to 62-m depth. At a slightly deeper depth, a sharper Ce maximum is observed with concentrations exceeding 11 nM at a 67-m depth, immediately above the anoxic zone. The aquatic concentrations of REE reported here are ˜50-fold higher than previously reported for marine oxic/anoxic boundaries and are, to our knowledge, the highest ever observed at natural oxic/anoxic interfaces. REE maxima occur within stable and warm saline waters. All REE concentrations decrease sharply in the sulfidic bottom waters. The redox-cline in Lake Vanda is dominated by diffusional processes and vertical transport of dissolved species driven by concentration

  4. Assessing rare earth elements in quartz rich geological samples.

    PubMed

    Santoro, A; Thoss, V; Guevara, S Ribeiro; Urgast, D; Raab, A; Mastrolitti, S; Feldmann, J

    2016-01-01

    Sodium peroxide (Na2O2) fusion coupled to Inductively Coupled Plasma Tandem Mass Spectrometry (ICP-MS/MS) measurements was used to rapidly screen quartz-rich geological samples for rare earth element (REE) content. The method accuracy was checked with a geological reference material and Instrumental Neutron Activation Analysis (INAA) measurements. The used mass-mode combinations presented accurate results (only exception being (157)Gd in He gas mode) with recovery of the geological reference material QLO-1 between 80% and 98% (lower values for Lu, Nd and Sm) and in general comparable to INAA measurements. Low limits of detection for all elements were achieved, generally below 10 pg g(-1), as well as measurement repeatability below 15%. Overall, the Na2O2/ICP-MS/MS method proved to be a suitable lab-based method to quickly and accurately screen rock samples originating from quartz-rich geological areas for rare earth element content; particularly useful if checking commercial viability. PMID:26595776

  5. Germanium and Rare Earth Element accumulation in woody bioenergy crops

    NASA Astrophysics Data System (ADS)

    Hentschel, Werner

    2016-04-01

    Germanium and REEs are strategic elements that are used for high tech devices and engineered systems, however these elements are hardly concentrated into mineable ore deposits. Since these elements occur widely dispersed in the earth crust with concentrations of several mgṡkg‑1 (Ge 1.6 mgṡkg‑1, Nd 25 mgṡkg‑1) a new possibility to gain these elements could be phytomining, a technique that uses plants to extract elements from soils via their roots. Since knowledge about accumulating plant species is quite limited we conducted research on the concentrations of strategic elements in wood and leaves of fast growing tree species (Salix spec., Populus spec., Betula pendula, Alnus glutinosa, Fraxinus excelsior, Acer pseudoplatanus). In total 35 study sites were selected in the mining affected area around Freiberg (Saxony, Germany), differing in their species composition and degree of contamination with toxic trace metals (Pb, As, Cd). On each site plant tissues (wood and leaves, respectively) of different species were sampled. In addition soil samples were taken from a soil depth of 0 - 30 cm and 30 - 60 cm. The aim of our work was to investigate correlations between the concentrations of the target elements in plant tissues and soil characteristics like pH, texture, nutrients and concentrations in six operationally defined soil fractions (mobile, acid soluble, oxidizable, amorphic oxides, crystalline oxides, residual or siliceous). Concentrations of elements in soil extracts and plant tissues were measured with ICP-MS. The element Nd was selected as representative for the group of REEs, since this element showed a high correlation with the concentrations of the other REE We found that the concentration of Nd in the leaves (0.31 mgṡkg‑1Nd) were several times higher than in herbaceous species (0.05 mgṡkg‑1 Nd). The concentration of Ge in leaves were ten times lower than that of Nd whereas in herbaceous species Nd and Ge were in equal magnitude. Within

  6. Compositional and phase relations among rare earth element minerals

    NASA Technical Reports Server (NTRS)

    Burt, D. M.

    1989-01-01

    A review is presented that mainly treats minerals in which the rare-earth elements are essential constituents, e.g., bastnaesite, monazite, xenotime, aeschynite, allanite. The chemical mechanisms and limits of REE substitution in some rock-forming minerals (zircon, apatite, titanite, garnet) are also derived. Vector representation of complex coupled substitutions in selected REE-bearing minerals is examined and some comments on REE-partitioning between minerals as related to acid-based tendencies and mineral stabilities are presented. As the same or analogous coupled substitutions involving the REE occur in a wide variety of mineral structures, they are discussed together.

  7. Rare earth element patterns in biotite, muscovite and tourmaline minerals

    SciTech Connect

    Laul, J.C.; Lepel, E.A.

    1986-04-21

    Rare earth element concentrations in the minerals biotite and muscovite from the mica schist country rocks of the Etta pegmatite and tourmalines from the Bob Ingersoll pegmatite have been measured by INAA and CNAA. The concentrations range from 10/sup -4/ g/g to 10/sup -10g//sub g/. The REE patterns of biotite, muscovite and tourmaline reported herein are highly fractionated from light to heavy REE. The REE concentrations in biotite and muscovite are high and indigenous. The pegmatite tourmalines contain low concentrations of REE. Variations in tourmaline REE patterns reflect the geochemical evolution of pegmatite melt/fluid system during crystallization.

  8. Heavy elements Ba, La, Ce, Nd, and Eu in 56 Galactic bulge red giants

    NASA Astrophysics Data System (ADS)

    Van der Swaelmen, M.; Barbuy, B.; Hill, V.; Zoccali, M.; Minniti, D.; Ortolani, S.; Gómez, A.

    2016-01-01

    Aims: The aim of this work is the study of abundances of the heavy elements Ba, La, Ce, Nd, and Eu in 56 bulge giants (red giant branch and red clump) with metallicities ranging from -1.3 dex to 0.5 dex. Methods: We obtained high-resolution spectra of our giant stars using the FLAMES-UVES spectrograph on the Very Large Telescope. We inspected four bulge fields along the minor axis. Results: We measure the chemical evolution of heavy elements, as a function of metallicity, in the Galactic bulge. Conclusions: The [Ba,La,Ce,Nd/Fe] vs. [Fe/H] ratios decrease with increasing metallicity, in which aspect they differ from disc stars. In our metal-poor bulge stars, La and Ba are enhanced relative to their thick disc counterpart, while in our metal-rich bulge stars La and Ba are underabundant relative to their disc counterpart. Therefore, this contrast between bulge and discs trends indicates that bulge and (solar neighbourhood) thick disc stars could behave differently. An increase in [La,Nd/Eu] with increasing metallicity, for metal-rich stars with [Fe/H] > 0 dex, may indicate that the s-process from AGB stars starts to operate at a metallicity around solar. Finally, [Eu/Fe] follows the [α/ Fe] behaviour, as expected, since these elements are produced by SNe type II. Observations collected at the European Southern Observatory, Paranal, Chile (ESO programmes 71.B-0617A, 73.B0074A, and GTO 71.B-0196)

  9. Rare earth element geochemistry of massive sulfides-sulfates and gossans on the Southern Explorer Ridge

    SciTech Connect

    Barrett, T.J. ); Jarvis, I. ); Jarvis, K.E. )

    1990-07-01

    Massive sulfide-sulfate deposits on the Southern Explorer Ridge were analyzed for 14 rare earth elements (REE) by a modified inductively coupled plasma-mass spectrometric technique that included a correction for high Ba content. Bulk samples of finely intermixed sulfides, sulfate, and amorphous silica contain {Sigma}REE concentrations of {le} 6 ppm. REE patterns range from (1) strongly enriched in light REE with positive Eu anomalies, to (2) relatively flat with positive Eu anomalies and slightly negative Ce anomalies, to (3) slightly enriched in light REE with moderately negative Ce anomalies. Pattern 1 is similar to that of 300-350 C solutions discharging at vents on the East Pacific Rise and the Mid-Atlantic Ridge, whereas pattern 3 resembles REE distributions in normal oceanic bottom waters. The sulfide-sulfate patterns are interpreted to result from variable mixtures of hydrothermal and normal seawater. Barite in gossans capping the mounds has an REE pattern almost identical to patterns of high-temperature vent solutions. Hydrothermal barite has lower REE contents and a different REE pattern relative to hydrogenous barite formed slowly on the sea floor.

  10. The estuarine geochemistry of rare earth elements and indium in the Chao Phraya River, Thailand

    NASA Astrophysics Data System (ADS)

    Nozaki, Yoshiyuki; Lerche, Dorte; Alibo, Dia Sotto; Snidvongs, Anond

    2000-12-01

    A new filtration method using a 0.04 μm hollow fiber filter was applied to the river, estuarine, and coastal waters in the Chao Phraya estuary for geochemical investigation. The filtered waters were analyzed for all the lanthanides, Y and In by using inductively coupled plasma mass spectrometry (ICPMS). The dissolved concentrations of rare earth elements (REEs) are significantly lower than those reported previously for other rivers, presumably because of effective removal of river colloids by the ultra-filtration. The variation of dissolved REEs in the estuary is dependent on the season. The light REEs vary considerably in the low salinity ( S < 3) zone presumably due to adsorption-desorption interaction with suspended particles. In January when the river discharge is low, the REEs show maxima in the mid salinity ( S = 5-12) zone suggesting that dissolved REEs are supplied to the waters by either desorption from suspended loads or remineralization of underlying sediments. The rapid removal of the REEs is also taking place in the turbid-clear water transition zone ( S = 12-15), presumably due to biological uptake associated with blooming of Noctilca occurred at the time of January sampling. In the medium to high discharge season (July and November), the dissolved REE(III)s at S > 3 show almost conservative trends being consistent with some of the previous works. Europium is strongly enriched in the river and estuarine waters compared to the South China Sea waters. Thus, the REE source of the Chao Phraya River must be fractionated and modified in entering to the South China Sea. Dissolved In and Ce in the high salinity ( S = 20-25) zone of the estuary are lower than those of the offshore waters, and therefore, the dissolved flux of the Chao Phraya River cannot account for the higher concentrations of dissolved In and Ce in the surface waters of the South China Sea. The negative Ce anomaly is progressively developed with increasing salinity, being consistent with

  11. Distribution and Geochemistry of Rare-Earth Elements in Rivers of Southern and Eastern Primorye (Far East of Russia)

    NASA Astrophysics Data System (ADS)

    Chudaev, O. V.; Bragin, I. V.; A, Kharitonova N.; Chelnokov, G. A.

    2016-03-01

    The distribution and geochemistry of rare earth elements (REE) in anthropogenic, technogenic and natural surface waters of southern and eastern Primorye, Far East of Russia, are presented in this study. The obtained results indicated that most of REE (up to 70%) were transported as suspended matter, ratio between dissolved and suspended forms varing from the source to the mouth of rivers. It is shown that all REE (except Ce) in the source of the rivers are predominantly presented in dissolved form, however, the content of light and heavy REE is different. Short-term enrichment of light rare earth elements (LREE) caused by REE-rich runoff from waste dumps and mining is neutralized by the increase in river flow rate. Rivers in urban areas are characterized by high content of LREE in dissolved form and very low in suspended one.

  12. Mimicking the magnetic properties of rare earth elements using superatoms

    PubMed Central

    Cheng, Shi-Bo; Berkdemir, Cuneyt; Castleman, A. W.

    2015-01-01

    Rare earth elements (REs) consist of a very important group in the periodic table that is vital to many modern technologies. The mining process, however, is extremely damaging to the environment, making them low yield and very expensive. Therefore, mimicking the properties of REs in a superatom framework is especially valuable but at the same time, technically challenging and requiring advanced concepts about manipulating properties of atom/molecular complexes. Herein, by using photoelectron imaging spectroscopy, we provide original idea and direct experimental evidence that chosen boron-doped clusters could mimic the magnetic characteristics of REs. Specifically, the neutral LaB and NdB clusters are found to have similar unpaired electrons and magnetic moments as their isovalent REs (namely Nd and Eu, respectively), opening up the great possibility in accomplishing rare earth mimicry. Extension of the superatom concept into the rare earth group not only further shows the power and advance of this concept but also, will stimulate more efforts to explore new superatomic clusters to mimic the chemistry of these heavy atoms, which will be of great importance in designing novel building blocks in the application of cluster-assembled nanomaterials. Additionally, based on these experimental findings, a novel “magic boron” counting rule is proposed to estimate the numbers of unpaired electrons in diatomic LnB clusters. PMID:25848014

  13. Mimicking the magnetic properties of rare earth elements using superatoms.

    PubMed

    Cheng, Shi-Bo; Berkdemir, Cuneyt; Castleman, A W

    2015-04-21

    Rare earth elements (REs) consist of a very important group in the periodic table that is vital to many modern technologies. The mining process, however, is extremely damaging to the environment, making them low yield and very expensive. Therefore, mimicking the properties of REs in a superatom framework is especially valuable but at the same time, technically challenging and requiring advanced concepts about manipulating properties of atom/molecular complexes. Herein, by using photoelectron imaging spectroscopy, we provide original idea and direct experimental evidence that chosen boron-doped clusters could mimic the magnetic characteristics of REs. Specifically, the neutral LaB and NdB clusters are found to have similar unpaired electrons and magnetic moments as their isovalent REs (namely Nd and Eu, respectively), opening up the great possibility in accomplishing rare earth mimicry. Extension of the superatom concept into the rare earth group not only further shows the power and advance of this concept but also, will stimulate more efforts to explore new superatomic clusters to mimic the chemistry of these heavy atoms, which will be of great importance in designing novel building blocks in the application of cluster-assembled nanomaterials. Additionally, based on these experimental findings, a novel "magic boron" counting rule is proposed to estimate the numbers of unpaired electrons in diatomic LnB clusters. PMID:25848014

  14. Bacterial Cell Surface Adsorption of Rare Earth Elements

    NASA Astrophysics Data System (ADS)

    Jiao, Y.; Park, D.; Reed, D.; Fujita, Y.; Yung, M.; Anderko, A.; Eslamimanesh, A.

    2015-12-01

    Rare earth elements (REE) play a critical role in many emerging clean energy technologies, including high-power magnets, wind turbines, solar panels, hybrid/electric vehicle batteries and lamp phosphors. In order to sustain demand for such technologies given current domestic REE shortages, there is a need to develop new approaches for ore processing/refining and recycling of REE-containing materials. To this end, we have developed a microbially-mediated bioadsorption strategy with application towards enrichment of REE from complex mixtures. Specifically, the bacterium Caulobacter crescentus was genetically engineered to display lanthanide binding tags (LBTs), short peptides that possess high affinity and specificity for rare earth elements, on its cell surface S-layer protein. Under optimal conditions, LBT-displayed cells adsorbed greater than 5-fold more REE than control cells lacking LBTs. Competition binding experiments with a selection of REEs demonstrated that our engineered cells could facilitate separation of light- from heavy- REE. Importantly, binding of REE onto our engineered strains was much more favorable compared to non-REE metals. Finally, REE bound to the cell surface could be stripped off using citrate, providing an effective and non-toxic REE recovery method. Together, this data highlights the potential of our approach for selective REE enrichment from REE containing mixtures.

  15. Trace elemental imaging of rare earth elements discriminates tissues at microscale in flat fossils.

    PubMed

    Gueriau, Pierre; Mocuta, Cristian; Dutheil, Didier B; Cohen, Serge X; Thiaudière, Dominique; Charbonnier, Sylvain; Clément, Gaël; Bertrand, Loïc

    2014-01-01

    The interpretation of flattened fossils remains a major challenge due to compression of their complex anatomies during fossilization, making critical anatomical features invisible or hardly discernible. Key features are often hidden under greatly preserved decay prone tissues, or an unpreparable sedimentary matrix. A method offering access to such anatomical features is of paramount interest to resolve taxonomic affinities and to study fossils after a least possible invasive preparation. Unfortunately, the widely-used X-ray micro-computed tomography, for visualizing hidden or internal structures of a broad range of fossils, is generally inapplicable to flattened specimens, due to the very high differential absorbance in distinct directions. Here we show that synchrotron X-ray fluorescence spectral raster-scanning coupled to spectral decomposition or a much faster Kullback-Leibler divergence based statistical analysis provides microscale visualization of tissues. We imaged exceptionally well-preserved fossils from the Late Cretaceous without needing any prior delicate preparation. The contrasting elemental distributions greatly improved the discrimination of skeletal elements material from both the sedimentary matrix and fossilized soft tissues. Aside content in alkaline earth elements and phosphorus, a critical parameter for tissue discrimination is the distinct amounts of rare earth elements. Local quantification of rare earths may open new avenues for fossil description but also in paleoenvironmental and taphonomical studies. PMID:24489809

  16. Trace Elemental Imaging of Rare Earth Elements Discriminates Tissues at Microscale in Flat Fossils

    PubMed Central

    Gueriau, Pierre; Mocuta, Cristian; Dutheil, Didier B.; Cohen, Serge X.; Thiaudière, Dominique; Charbonnier, Sylvain; Clément, Gaël; Bertrand, Loïc

    2014-01-01

    The interpretation of flattened fossils remains a major challenge due to compression of their complex anatomies during fossilization, making critical anatomical features invisible or hardly discernible. Key features are often hidden under greatly preserved decay prone tissues, or an unpreparable sedimentary matrix. A method offering access to such anatomical features is of paramount interest to resolve taxonomic affinities and to study fossils after a least possible invasive preparation. Unfortunately, the widely-used X-ray micro-computed tomography, for visualizing hidden or internal structures of a broad range of fossils, is generally inapplicable to flattened specimens, due to the very high differential absorbance in distinct directions. Here we show that synchrotron X-ray fluorescence spectral raster-scanning coupled to spectral decomposition or a much faster Kullback-Leibler divergence based statistical analysis provides microscale visualization of tissues. We imaged exceptionally well-preserved fossils from the Late Cretaceous without needing any prior delicate preparation. The contrasting elemental distributions greatly improved the discrimination of skeletal elements material from both the sedimentary matrix and fossilized soft tissues. Aside content in alkaline earth elements and phosphorus, a critical parameter for tissue discrimination is the distinct amounts of rare earth elements. Local quantification of rare earths may open new avenues for fossil description but also in paleoenvironmental and taphonomical studies. PMID:24489809

  17. Meteoritic Ce-138/Ce-142 ratio and its evolution

    NASA Astrophysics Data System (ADS)

    Shimizu, H.; Tanaka, T.; Masuda, A.

    1984-01-01

    Cerium isotope ratios were determined for Juvinas, Pasamonte and ALH-78132 eucrites and the Jilin (H4) chondrite. Neodymium isotope ratios and abundances of lanthanum, cerium, neodymium and samarium were also determined for these meteorites. The La-Ce isotopic system, coupled with the Sm-Nd system, provides a new isotope tracer for geo- and cosmo-chemical samples, especially for samples having a Ce anomaly in the rare-earth element patterns.

  18. Natural and anthropogenic rare earth elements in Lago de Paranoá, Brasilia, Brazil

    NASA Astrophysics Data System (ADS)

    Merschel, Gila; Baldewein, Linda; Bau, Michael; Dantas, Elton Luiz; Walde, Detlef; Bühn, Bernhard

    2014-05-01

    Rare earth elements (REE) belong to the group of particle reactive elements and occur at ultratrace levels in natural waters. They are exclusively trivalent, but Ce and Eu can also be tetravalent and divalent, respectively, depending on the redox-level, the pH and the temperature of the fluid. Due to these redox changes, normalized REE patterns may show Ce and/or Eu anomalies. Recently, these high-tech metals raised significant public attention, as they are of great economic importance and consumption and hence release into the environment increased sharply. The most prominent example of a REE contamination is anthropogenic Gd, which is derived from Gd-based contrast agents used in magnetic resonance imaging. Due to their high stabilities, these compounds are not readily removed by commonly applied waste water treatment technologies and, therefore, are released from treatment plants into surface and ground waters. Hence, this anthropogenic Gd can be used as a tracer for the presence of waste water-derived substances such as pharmaceuticals and personal care products in river, lake, ground and tap waters. Lago de Paranoá is an artificial reservoir lake in the city of Brasilia, Brazil, and is currently considered a potential freshwater resource. The city's two waste water treatment plants are located on its shore and their effluents are discharged into the lake. To investigate the level of contamination, we took water samples at 11 stations in the lake and compared the REE concentrations in unfiltered and filtered (<200 nm) lake water. The unfiltered water samples show light REE enrichment (LaSN/YbSN: 1.37-1.98) and high REE concentrations (Sum REE: 192 - 476 ng/L), while the unfiltered water samples are heavy REE enriched (LaSN/YbSN: 0.15-0.61) at lower concentrations (Sum REE: 50 - 85 ng/L). This is due to the fact that light REE are preferentially bound to particle surfaces, while the heavy REE are preferentially complexed with ligands in solution. In marked

  19. Simultaneous determination of rare earth elements in ore and anti-corrosion coating samples using a portable capillary electrophoresis instrument with contactless conductivity detection.

    PubMed

    Nguyen, Thi Anh Huong; Nguyen, Van Ri; Le, Duc Dung; Nguyen, Thi Thanh Binh; Cao, Van Hoang; Nguyen, Thi Kim Dung; Sáiz, Jorge; Hauser, Peter C; Mai, Thanh Duc

    2016-07-29

    The employment of an in-house-made capillary electrophoresis (CE) instrument with capacitively coupled contactless conductivity detection (C(4)D) as a simple and inexpensive solution for simultaneous determination of many rare earth elements (REEs) in ore samples from Vietnam, as well as in anti-corrosion coating samples is reported. 14 REEs (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) were determined using an electrolyte composed of 20mM arginine and 10mM α-hydroxyisobutyric acid adjusted to pH 4.2 with acetic acid. The best detection limit achieved was 0.24mg/L using the developed CE-C(4)D method. Good agreement between results from CE-C(4)D and the confirmation method (ICP-MS) was achieved, with a coefficient of determination (r(2)) for the two pairs of data of 0.998. PMID:27363736

  20. Distribution of rare earth elements in an alluvial aquifer affected by acid mine drainage: the Guadiamar aquifer (SW Spain).

    PubMed

    Olías, M; Cerón, J C; Fernández, I; De la Rosa, J

    2005-05-01

    This work analyses the spatial distribution, the origin, and the shale-normalised fractionation patterns of the rare earth elements (REE) in the alluvial aquifer of the Guadiamar River (south-western Spain). This river received notoriety in April 1998 for a spill that spread a great amount of slurry (mainly pyrites) and acid waters in a narrow strip along the river course. Groundwaters and surface waters were sampled to analyse, among other elements, the REEs. Their spatial distribution shows a peak close to the mining region, in an area with low values of pH and high concentrations of sulphates and other metals such as Zn, Cu, Co, Ni, Pb, and Cd. The patterns of shale-normalised fractionation at the most-contaminated points show an enrichment in the middle rare earth elements (MREE) with respect to the light (LREE) and heavy (HREE) ones, typical of acid waters. The Ce-anomaly becomes more negative as pH increases, due to the preferential fractionation of Ce in oxyhydroxides of Fe. PMID:15701392

  1. Key Factors Controlling Space- and Time-Linked Rare Earth Element Distribution in Shallow Groundwaters

    NASA Astrophysics Data System (ADS)

    Dia, A.; Gruau, G.; Olivie-Lauquet, G.; Henin, O.; Petitjean, P.; Le Coz-Bouhnik, M.

    2001-12-01

    This study investigates the effects of source-rock composition, redox changes and organic matter on the hydrochemistry of Rare Earth Elements (REE). Wetland groundwater samples as well as upland zone water samples were recovered weekly over a six month period (January to June 1999) from a small catchment (Petit Hermitage, France). The samples were filtered on the field using membrane filters of 0.22 μ m pore size, and then analyzed for their Dissolved Organic Carbon (DOC) as well as Fe, Mn, Al, Th, U and REE concentrations. The results are discussed in conjunction with previous published DOC and trace-element concentrations obtained on comparable samples from three other small catchments, namely : the Nsimi-Zoetele, Goyoum (both in Cameroon) and Kervidy/Coet-Dan (France) catchments (Viers et al., 1997; Braun et al., 1998; Dia et al., 2000). Despite marked differences (such as bioclimatic conditions, vegetation cover, basement rock composition or human activity), results are surprisingly similar with always the occurrence of two spatially distinct groundwater types including : (i) a shallow, organic-rich groundwater below wetlands recording high and variable REE contents and displaying slight or no negative Ce anomaly. In the wetland groundwaters, the REE and other trace-element concentrations seem to be controlled by seasonal dynamics, involving both temperature, whose onset at spring leads to higher organic carbon decomposition rates by microbial mass, and redox changes resulting in REE and other-trace element release in water when mineral phases occur to dissolve. (ii) The second groundwater type corresponds to a shallow, organic-poor groundwater type located below the hillslope domains. This second groundwater type displays lower REE (and other trace-element) concentrations, but distinguish from the former by the occurrence of very strong negative Ce anomalies, whose amplitude is variable, but appears to be linked to the sampling location along the catena. The

  2. The elements of the Earth's magnetism and their secular changes between 1550 and 1915

    NASA Technical Reports Server (NTRS)

    Fritsche, H.

    1983-01-01

    The results of an investigation about the magnetic agents outside the Earth's surface as well as the Earth's magnetic elements for the epochs 1550, 1900, 1915 are presented. The secular changes of the Earth's magnetic elements during the time interval 1550 - 1900 are also included.

  3. Influence of yttrium content on the location of rare earth ions in LYSO:Ce crystals

    SciTech Connect

    Ding, Dongzhou; Weng, Linhong; Yang, Jianhua; Ren, Guohao; Wu, Yuntao

    2014-01-15

    Single-crystal X-ray diffraction (SCD), X-ray fluorescence (XRF), inductively coupled plasma optical emission spectroscopy (ICP-OES) and X-ray excited luminescence (XEL) measurements were performed to investigate structure details and segregation coefficients of (Lu{sub 1−x}Y{sub x}){sub 2}SiO{sub 5}:Ce (x=0 at%, 8.7 at%, 25.7 at%, 44.7 at%, 65.7 at%, 87.9 at% and 100 at%). Y{sup 3+} cations were found to have a preferential occupation for RE1 site (7-oxygen-coordinated) over RE2 site (6-oxygen-coordinated), which results in a greater increase of cell parameter c than that of a with increase in Y content due to LYSO's microstructure characteristics. Results presented here revealed that the less the difference in electronegativity and effective ionic radius between the two ions, the easier substitution of one ion by the other, and hence the higher segregation coefficients. Besides, the contribution of luminescence of Ce1 and Ce2 in the whole XEL was evaluated, and the location of Ce{sup 3+} ion was discussed. - Graphical abstract: Segregation coefficients of (Lu{sub 1−x}Y{sub x}){sub 2}SiO{sub 5}:Cce:italic> at RT/ce:italic>. Display Omitted.

  4. Effect of rare earth Ce on the far infrared radiation property of iron ore tailings ceramics

    SciTech Connect

    Liu, Jie; Meng, Junping; Liang, Jinsheng; Duan, Xinhui; Huo, Xiaoli; Tang, Qingguo

    2015-06-15

    Highlights: • Detailed process proposed for preparation of iron ore tailings ceramics. • Replace natural minerals with iron ore tailings as raw materials for preparing functional ceramics. • Impact mechanism of Ce on far infrared ceramics, as well as its optimum addition amounts can be obtained. • Propose a new perspective on considering the mechanism of far infrared radiation. - Abstract: A kind of far infrared radiation ceramics was prepared by using iron ore tailings, CaCO{sub 3} and SiO{sub 2} as main raw materials, and Ce as additive. The result of Fourier transform infrared spectroscopy showed that the sample exhibits excellent radiation value of 0.914 when doping 7 wt.% Ce. Ce{sup 4+} dissolved into iron diopside and formed interstitial solid solution with it sintered at 1150 °C. The oxidation of Fe{sup 2+} to Fe{sup 3+} caused by Ce{sup 4+} led to a decrease of crystallite sizes and enhancement of Mg–O and Fe–O vibration in iron diopside, which consequently improved the far infrared radiation properties of iron ore tailings ceramics.

  5. The Future of Using Earth-Abundant Elements in Counter Electrodes for Dye-Sensitized Solar Cells.

    PubMed

    Briscoe, Joe; Dunn, Steve

    2016-05-01

    With limited global resources for many of the elements that are found in some of the most common renewable energy technologies, there is a growing need to use "Earth-abundant" elements as a long-term solution to growing energy demands. The dye-sensitized solar cell has the potential to produce low-cost renewable energy, with inexpensive production and most components using Earth-abundant elements. However, the most commonly used material for the cell counter electrode (CE) is platinum, an extremely expensive and rare element. A selection of the materials investigated as alternative CEs are discussed, including metal sulfides, oxides, carbides, and nitrides and carbon-based materials such as carbon nanotubes, graphene, and conductive polymers. As well as having the potential for lower cost, these materials can also produce more-efficient devices due to their high surface area and catalytic activity. Therefore, once issues such as stability have been studied in more detail and scale-up of production methods are considered, there is a very promising future for the replacement of Pt in DSSCs with lower-cost, Earth-abundant alternatives. PMID:26727984

  6. Core-Mantle Partitioning of Volatile Elements and the Origin of Volatile Elements in Earth and Moon

    NASA Technical Reports Server (NTRS)

    Righter, K.; Pando, K.; Danielson, L.; Nickodem, K.

    2014-01-01

    Depletions of siderophile elements in mantles have placed constraints on the conditions on core segregation and differentiation in bodies such as Earth, Earth's Moon, Mars, and asteroid 4 Vesta. Among the siderophile elements there are a sub-set that are also volatile (volatile siderophile elements or VSE; Ga, Ge, In, As, Sb, Sn, Bi, Zn, Cu, Cd), and thus can help to constrain the origin of volatile elements in these bodies, and in particular the Earth and Moon. One of the fundamental observations of the geochemistry of the Moon is the overall depletion of volatile elements relative to the Earth, but a satisfactory explanation has remained elusive. Hypotheses for Earth include addition during accretion and core formation and mobilized into the metallic core, multiple stage origin, or addition after the core formed. Any explanation for volatile elements in the Earth's mantle must also be linked to an explanation of these elements in the lunar mantle. New metal-silicate partitioning data will be applied to the origin of volatile elements in both the Earth and Moon, and will evaluate theories for exogenous versus endogenous origin of volatile elements.

  7. Elemental processes of transport and energy conversion in Earth's magnetosphere

    NASA Astrophysics Data System (ADS)

    Angelopoulos, Vassilis

    In the last 5 years observations from several missions and ground based observatories have honed in on the most elemental aspects of flux transport and energy conversion. Dipolarization fronts and their counterpart in the distant magnetotail "anti-dipolarization" fronts, which together are refered to herein as "reconnection fronts", usher the recently reconnected flux tubes from the near-Earth X-points and in the process convert magnetic energy to particle energy and wave radiation. On the tailward side they are responsible for plasmoid formation and acceleration. On the earthward side they result in elemental substorm current wedges or wedglets, which were initially postulated from ground observations alone. Recent observations have revealed how the interaction of wedgelets and the inner magnetosphere takes place. Questions remain with regards to the physics of the energy transfer process from global magnetic energy to local heating and waves, and with regards to the initiation of the X-point activations in space. Observations indicate that the latter may be induced by polar cap or dayside activity, suggesting a direct link between dayside reconnection and nightside phenomena. The likely causal sequence of events and open questions in light of these recent observations, and the field's outlook in anticipation of upcoming coordinated observations from the international Heliophysics System Observatory will be discussed.

  8. Rare earth-copper-magnesium compounds RECu 9Mg 2 ( RE=Y, La-Nd, Sm-Ho, Yb) with ordered CeNi 3-type structure

    NASA Astrophysics Data System (ADS)

    Solokha, P.; Pavlyuk, V.; Saccone, A.; De Negri, S.; Prochwicz, W.; Marciniak, B.; Różycka-Sokołowska, E.

    2006-10-01

    A series of ternary compounds RECu 9Mg 2 ( RE=Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Yb) have been synthesized via induction melting of elemental metal ingots followed by annealing at 400 °C for 4 weeks. Scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDXS) was used for examining microstructure and phase composition. These phases crystallize with an ordered version of the binary hexagonal structure type first reported for CeNi 3. The crystal structure was solved for TbCu 9Mg 2 from single crystal X-ray counter data (TbCu 9Mg 2-structure type, P6 3/mmc-space group, hP24-Pearson symbol, a=0.49886 (7) nm, c=1.61646 (3) nm, RF=0.0474 for 190 unique reflections). The Rietveld refinement of the X-ray powder diffraction patterns of RECu 9Mg 2 confirmed the same crystal structure for the reported rare earth metals. The unit cell volumes for RECu 9Mg 2 smoothly follow the lanthanide contraction. The existence of a RECu 9Mg 2 phase was excluded for RE=Er and Tm under the investigated experimental conditions.

  9. Rare earth element analysis indicates micropollutants in an urban estuary

    NASA Astrophysics Data System (ADS)

    Mohajerin, T. J.; Johannesson, K. H.; Kolker, A.; Burdige, D. J.; Chevis, D.

    2011-12-01

    Rare earth element analysis of Bayou Bienvenue waters shows anomalously high gadolinium, Gd, concentrations relative to its nearest neighbors in the REE series, europium and terbium. The anomalously high Gd concentrations indicate anthropogenic input from waste-water treatment plants in the area as anthropogenic Gd input can be traced back to its use as a contrast agent in magnetic resonance imaging in hospitals. Others have shown that anomalously high levels of Gd in natural waters are likely to be associated with other micropollutants that also occur in hospital effluent and that are not removed in the wastewater treatment process, including pharmaceuticals in the form of steroids, antihistamines, and antibiotics. Estuaries serve as many important ecological roles and have been shown to act as a filter for pollutants. To better understand the transport, biogeochemical cycling, and ultimate fate of trace elements in estuaries, I collected surface water samples from Bayou Bienvenue, a wetland triangle that covers an area of 427 acres directly adjacent to New Orleans, Louisiana. Water samples from Bayou Bienvenue were collected along the salinity gradient and subsequently filtered through progressively smaller pore-size filters. The resulting fractions were analyzed for trace element concentions, including the REEs, by magnetic sector ICP-MS. The attached figure shows the Gd anomaly present in the particulate (>0.45μm) fraction. Upper continental crust (UCC)-normalized plots of colloidal REEs (0.02μm - 0.45μm) fraction is lacking this anomaly indicating anthropogenic Gd is found chiefly in the particulate fraction in Bayou Bienvenue. No clear relationship between Gd concentration and salinity was apparent.

  10. Rare earth elements in pore waters from Cabo Friós western boundary upwelling system

    NASA Astrophysics Data System (ADS)

    Smoak, J. M.; Silva-Filho, E. V.; Rousseau, T.; Albuquerque, A. L.; Caldeira, P. P.; Moreira, M.

    2015-12-01

    Rare earth elements (REE) are a group of reactive trace elements in aqueous media, they have a coherent chemical behavior with however a subtle and gradual shift in physicochemical properties allowing their use as tracers of sources and processes. Uncertainties on their oceanic inputs and outputs still remains [Arsouze et al., 2009; Siddall et al., 2008; Tachikawa et al., 2003]. The water-sediment interface were early on identified as a relevant REE source due to the high distribution coefficient between sediments and pore waters [Elderfield and Sholkovitz, 1987] and substantially higher concentration then the water column [Abbott et al., 2015; Haley et al., 2004; Sholkovitz et al., 1989; Soyol-Erdene and Huh, 2013]. Here we present a cross shelf transect of 4 short pore waters REE profiles on a 680 km2 mud bank located in the region of Cabo Frio, Brazil. This study reveals similar trends at the four sites: a REE production zone reflected by a maximum in concentration at the top of the sediment evolving with depth toward a REE consumption zone reflected by a minimum in REE concentrations. PAAS normalized patterns shows 1) a progressive depletion in LREE with depth with HREE/LREE ratios comprised between 1.1 and 1.6 in the 2 first centimeters evolving gradually to ratios comprised between 2.8 and 4.7 above 7 cm 2) A sharp gradient in negative Ce anomaly with Ce/Ce* values reaching 0.3. With maximum Nd concentrations comprised between 780 and 1200 pmol.kg and considering that seawater Nd concentrations of Brazilian shelf bottom waters are comprised between 24 and 50 pmol.Kg-1 we apply the Fick´s First Law of diffusion and estimate that 340 +/- 90 nmol. m-2 Y-1 of Nd is released in the Cabo frio´s mudbank. This flux is in the same order of magnitude of recent estimates by [Abbott et al., 2015] in the slope of Oregon´s margin. Unraveling processes responsible for the REE production zone will help to refine the global REE fluxes estimates.

  11. Alkaline-earth oxide network modifier on optical properties of Ce3+-activated borogermanate glasses

    NASA Astrophysics Data System (ADS)

    Sun, Xin-Yuan; Xiao, Zhuo-Hao; Zhong, Jiu-Ping

    2015-12-01

    Transparent and colorless CeO2-activated borogermanate glasses, with the nominal composition of 25B2O3-40GeO2-14Gd2O3-1CeO2-20MO (M = Ba, Sr, Ca and Mg), were synthesized by a melt-quenching method in air. Their optical properties including the transmittance, photoluminescence (excitation and emission spectra), the luminescence decay curves, as well as the temperature-dependent emission spectra were studied in detail. The room temperature photoluminescence spectra reveal that the emission intensity of the MgO glass is about two times stronger than that of the BaO glass. The blue shift of the cut-off edge, excitation and emission spectra of Ce3+-activated borogermanate glass were clearly observed in the order of BaO, SrO, CaO and MgO. And the emission intensity of Ce3+ ions as a function of temperature range in 325-475 K was also investigated.

  12. Rare earth elements exploitation, geopolitical implications and raw materials trading

    NASA Astrophysics Data System (ADS)

    Chemin, Marie-Charlotte

    2015-04-01

    Rare earth elements (REE) correspond to seventeen elements of the periodic table. They are used in high technology, cracking, electric cars' magnet, metal alloy for batteries, and also in phone construction or ceramics for electronic card. REEs are an important resource for high technology. This project targets 16 years old students in the subject "personalized aid" and will last six weeks. The purpose of this project is to develop autonomy and research in groups for a transdisciplinary work. This project gathers knowledge in geology, geography and economics. During the first session students analyze the geology applications of the REE. They begin the analysis with learning the composition in different rocks such as basalt and diorite to make the link with crystallization. Then they compare it with adakite to understand the formation of these rocks. In the second session, they study REE exploitation. We can find them as oxides in many deposits. The principal concentrations of rare earth elements are associated with uncommon varieties of igneous rocks, such as carbonatites. They can use Qgis, to localize this high concentration. In the third session, they study the environmental costs of REE exploitation. Indeed, the exploitation produces thorium and carcinogenic toxins: sulphates, ammonia and hydrochloric acid. Processing one ton of rare earths produces 2,000 tons of toxic waste. This session focuses, first, on Baotou's region, and then on an example they are free to choose. In the fourth session, they study the geopolitical issues of REE with a focus on China. In fact this country is the largest producer of REE, and is providing 95% of the overall production. REE in China are at the center of a geopolitical strategy. In fact, China implements a sort of protectionism. Indeed, the export tax on REE is very high so, as a foreign company, it is financially attractive to establish a manufacturing subsidiary in China in order to use REE. As a matter of fact

  13. Global in-use stocks of the rare Earth elements: a first estimate.

    PubMed

    Du, Xiaoyue; Graedel, T E

    2011-05-01

    Even though rare earth metals are indispensible in modern technology, very little quantitative information other than combined rare earth oxide extraction is available on their life cycles. We have drawn upon published and unpublished information from China, Japan, the United States, and elsewhere to estimate flows into use and in-use stocks for 15 of the metals: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y. Here, we show that the combined flows into use comprised about 90 Gg in 2007; the highest for individual metals were ∼28 Gg Ce and ∼22 Gg La, the lowest were ∼0.16 Gg Tm and ∼0.15 Gg Lu. In-use stocks ranged from 144 Gg Ce to 0.2 Gg Tm; these stocks, if efficiently recycled, could provide a valuable supplement to geological stocks. PMID:21438595

  14. Rare Earth Element Partitioning in Lunar Minerals: An Experimental Study

    NASA Technical Reports Server (NTRS)

    McIntosh, E. C.; Rapp, J. F.; Draper, D. S.

    2016-01-01

    The partitioning behavior of rare earth elements (REE) between minerals and melts is widely used to interpret the petrogenesis and geologic context of terrestrial and extra-terrestrial samples. REE are important tools for modelling the evolution of the lunar interior. The ubiquitous negative Eu anomaly in lunar basalts is one of the main lines of evidence to support the lunar magma ocean (LMO) hypothesis, by which the plagioclase-rich lunar highlands were formed as a flotation crust during differentiation of a global-scale magma ocean. The separation of plagioclase from the mafic cumulates is thought to be the source of the Eu depletion, as Eu is very compatible in plagioclase. Lunar basalts and volcanic glasses are commonly depleted in light REEs (LREE), and more enriched in heavy REEs (HREE). However, there is very little experimental data available on REE partitioning between lunar minerals and melts. In order to interpret the source of these distinctive REE patterns, and to model lunar petrogenetic processes, REE partition coefficients (D) between lunar minerals and melts are needed at conditions relevant to lunar processes. New data on D(sub REE) for plagioclase, and pyroxenes are now available, but there is limited available data for olivine/melt D(sub REE), particularly at pressures higher than 1 bar, and in Fe-rich and reduced compositions - all conditions relevant to the lunar mantle. Based on terrestrial data, REE are highly incompatible in olivine (i.e. D much less than 1), however olivine is the predominant mineral in the lunar interior, so it is important to understand whether it is capable of storing even small amounts of REE, and how the REEs might be fractionatied, in order to understand the trace element budget of the lunar interior. This abstract presents results from high-pressure and temperature experiments investigating REE partitioning between olivine and melt in a composition relevant to lunar magmatism.

  15. Geochemical behavior of rare earth elements and other trace elements in the Amazon River

    NASA Astrophysics Data System (ADS)

    Merschel, Gila; Bau, Michael; Dantas, Elton Luiz

    2014-05-01

    Rivers transport large amounts of dissolved and suspended particulate material from the catchment area to the oceans and are a major source of trace metals to seawater. The Amazon River is the world's largest river and supplies approximately 20% of the oceans' freshwater (Molinier et al., 1997). However, the behavior of trace elements, especially particle-reactive elements such as the rare earth elements (REE), within the river as well as in the estuary is not well constrained and rather little is known about their transport mechanisms. This study aims at understanding the transport properties of particle-reactive elements in the Amazon River and some of its major tributaries, including the Rio Solimões, Rio Negro, Tapajos, Xingu and Jari Rivers. Samples were taken at 12 stations, seven of which were located in the Amazon mainstream, while the other five stations sampled its tributaries. To account for the effects of variable discharge, the samples were collected during periods of high and low discharge. We present data for major and trace elements, including REE, of the dissolved and suspended load of these samples. First results indicate that the shale-normalized REE pattern of the dissolved load (filtered through 0.2 µm membranes) of the Amazon mainstream and the Rio Solimões confirm earlier studies (Elderfield et al., 1990; Gerard et al., 2003) and show an enrichment of the middle REE relative to the light and heavy REE (LaSN/GdSN: 0.25 - 0.32; GdSN/YbSN: 1.54 - 1.78). In contrast to the Amazon mainstream and the Rio Solimões, which are considered to be whitewater rivers, blackwater rivers, such as the Rio Negro, have a flat REE pattern with higher REE concentrations than whitewater rivers. The third water-type found in the Amazon Basin is clearwater, e.g. Rio Tapajos, with REE patterns in between those of the other two types, i.e. LaSN/GdSN: 0.55 - 0.70; GdSN/YbSN: 1.26 - 1.55. A similar behavior can be identified for other major and trace elements. While

  16. Effects of spraying rare earths on contents of rare Earth elements and effective components in tea.

    PubMed

    Wang, Dongfeng; Wang, Changhong; Ye, Sheng; Qi, Hongtao; Zhao, Guiwen

    2003-11-01

    Rare earth (RE) fertilizer is widely applied in China to increase the yield and the quality of crops including tea. However, the effects of spraying RE fertilizer on the contents of rare earth elements (REE) and effective components in tea are unknown. The results from basin and field experiments show that the values of the REE concentrations in new shoots of tea plants and the concentration of REE in the soil (REE/REEs) either from control basins or from treatment basins were smaller than those in other parts of tea plant and similar between control and treatment. The longer the interval between spraying RE fertilizer and picking the shoots of tea plants, the less the effects from spraying. About 80% summation operator REE (the sum of the concentrations of 15 REE) in tea, whether it came from spraying or not, was insoluble in the infusion. About 10% the soluble REE of summation operator REE in tea infusion was bound to polysaccharide, and the amount of REE bound polysaccharide decreased over time. At least a 25 day safety interval is needed between spraying and picking if the microelement fertilizer is used, in order to enhance tea output and to ensure tea safety. PMID:14582968

  17. Size distribution of rare earth elements in coal ash

    USGS Publications Warehouse

    Scott, Clinton T.; Deonarine, Amrika; Kolker, Allan; Adams, Monique; Holland, James F.

    2015-01-01

    Rare earth elements (REEs) are utilized in various applications that are vital to the automotive, petrochemical, medical, and information technology industries. As world demand for REEs increases, critical shortages are expected. Due to the retention of REEs during coal combustion, coal fly ash is increasingly considered a potential resource. Previous studies have demonstrated that coal fly ash is variably enriched in REEs relative to feed coal (e.g, Seredin and Dai, 2012) and that enrichment increases with decreasing size fractions (Blissett et al., 2014). In order to further explore the REE resource potential of coal ash, and determine the partitioning behavior of REE as a function of grain size, we studied whole coal and fly ash size-fractions collected from three U.S commercial-scale coal-fired generating stations burning Appalachian or Powder River Basin coal. Whole fly ash was separated into , 5 um, to 5 to 10 um and 10 to 100 um particle size fractions by mechanical shaking using trace-metal clean procedures. In these samples REE enrichments in whole fly ash ranges 5.6 to 18.5 times that of feedcoals. Partitioning results for size separates relative to whole coal and whole fly ash will also be reported. 

  18. Magnetic structures and interplay between rare-earth Ce and Fe magnetism in single-crystal CeFeAsO

    SciTech Connect

    Zhang, Qiang; Tian, Wei; Li, Haifeng; Kim, Jong-Woo; Yan, Jiaqiang; McCallum, Robert William; Lograsso, Thomas A.; Zarestky, Jerel L.; Budko, Sergey L.; McQueeney, Robert J.; Vaknin, David

    2013-11-27

    Neutron and synchrotron resonant x-ray magnetic scattering (RXMS) complemented by heat capacity and resistivity measurements reveal the evolution of the magnetic structures of Fe and Ce sublattices in a CeFeAsO single crystal. The RXMS of magnetic reflections at the Ce LII edge shows a magnetic transition that is specific to the Ce antiferromagnetic long-range ordering at TCe≈ 4 K with short-range Ce ordering above TCe, whereas neutron diffraction measurements of a few magnetic reflections indicate a transition at T∗≈ 12 K with an unusual order parameter. Detailed order-parameter measurements on several magnetic reflections by neutrons show a weak anomaly at 4 K that we associate with the Ce ordering. The successive transitions at TCe and T∗ can also be clearly identified by two anomalies in heat capacity and resistivity measurements. The higher transition temperature at T∗≈ 12 K is mainly ascribed to Fe spin reorientation transition, below which Fe spins rotate uniformly and gradually in the ab plane. The Fe spin reorientation transition and short-range Ce ordering above TCe reflect the strong Fe-Ce couplings prior to long-range ordering of the Ce. The evolution of the intricate magnetic structures in CeFeAsO going through T∗ and TCe is proposed.

  19. Rare-earth element variation in phosphate nodules from midcontinent Pennsylvanian cyclothems

    SciTech Connect

    Kidder, D.L. . Dept. of Geological Sciences); Eddy-Dilek, C.A. . Savannah River Technology Center)

    1994-07-01

    The rare-earth element (REE) geochemistry of phosphate nodules from eastern Kansas and northeastern Oklahoma is dominated by patterns that are generally flat or are enriched in middle REE (MREE). Flat patterns are typical of phosphate nodules preserved in thick shales and in nodules from shales deposited nearest to detrital sources. The flat patterns are probably derived from terrigenous constituents in the host shale. MREE enrichment is evident in phosphate found in relatively thin shales and in distal shales. The authors suggest that the MREE-enriched pattern reflects the contribution of MREE-enriched fecal phosphate. The initial MREE enrichment mechanism may have been analogous to that in which some modern algae preferentially extract MREE from water of marine composition. The MREE-enriched signature may be preserved only in phosphate nodules that formed where terrigenous input was so low that it did not mask the characteristic fecal pattern. Rare Ce depletion patterns reflect a primary seawater REE source that has not been obscured by fecal or detrital components.

  20. A method for predicting bioavailability of rare earth elements in soils to maize.

    PubMed

    Wang, Wei-Sheng; Shan, Xiao-Quan; Wen, Bei; Zhang, Shu-Zhen

    2004-03-01

    A single-extraction procedure using low-molecular-weight organic acids (LMWOAs) as extractant and the first and second steps of a three-step extraction procedure recommended by the European Community Bureau of Reference (BCR; now European Community Standards, Measurement and Testing Programme, Brussels, Belgium) were performed to extract the light rare earth elements (LREEs) La, Ce, Pr, and Nd from wet rhizosphere soil. The extracted soil solutions were successively filtered through membranes with a pore size of less than 0.45 microm and a molecular weight cutoff of less than 1 kDa, which were termed colloidal and truly dissolved fractions, respectively. Apoplastically and symplastically bound LREEs in maize roots were experimentally distinguished by ultrasound-assisted desorption with 1 mM CaCl2 solution at 0 degrees C in ice-cooled water bath. When the LMWOAs extraction method was used, a good correlation was obtained between LREEs in soil colloidal and truly dissolved fractions and LREEs bound to apoplasm and symplasm of maize root. Both apoplastically and symplastically bound LREEs are the result of bioavailability. However, a poor correlation was obtained between LREEs in fractions water soluble, exchangeable and carbonate bound (B1) and Fe-Mn oxide bound (B2) of the BCR method and LREEs in apoplasm and symplasm and in intact roots. Hence, the LMWOAs extraction method is recommended for measuring the bioavailability of LREEs in soils. PMID:15285371

  1. Interoceanic variation in the rare earth, major, and trace element depositional chemistry of chert: Perspectives gained from the DSDP and ODP record

    SciTech Connect

    Murray, R.W.; Jones, D.L. ); Buchholtz Ten Brink, M.R.; Gerlach, D.C.; Russ, G.P. III )

    1992-05-01

    Rare earth element (REE), major, and trace element abundances and relative fractionations in forty nodular cherts sampled by the Deep Sea Drilling Project (DSDP) and Ocean Drilling Program (ODP) indicate that the REE composition of chert records the interplay between terrigenous sources and scavenging from the local seawater. Chert from the large Pacific Ocean, where deposition occurs relatively removed from significant terrigenous input, records a depositional REE signal dominated by adsorption of dissolved REEs from sea water. Chert from the Atlantic basin, a moderately sized ocean basin lined by passive margins and with more terrigenous input than the Pacific, records a mix of adsorptive and terrigenous REE signals, with moderately negative Ce anomalies and La{sub n}/YB{sub n} ratios intermediate to those of the Pacific and those of terrigenous input. Chert from the southern high latitude region is dominated by the large terrigenous input on the Antarctic passive margin, with inherited Ce/Ce{sup *} {approximately} 1 and inherited La{sub n}/Yb{sub n} values of {approximately} 1.2-1.4. This and previous studies of the large-scale controlling parameters of sedimentary REEs across ocean basins collectively indicate that REE indices of depositional regime (e.g., Ce/Ce{sup *}, La{sub n}/Yb{sub n}, La{sub ex}) are reproducible in a variety of sediment and rock lithologies, ages, and ocean basins, and present a coherent tool for paleoceanographic and tectonic basin reconstructions.

  2. Seawater-derived rare earth element addition to abyssal peridotites during serpentinization

    NASA Astrophysics Data System (ADS)

    Frisby, Carl; Bizimis, Michael; Mallick, Soumen

    2016-04-01

    Serpentinized abyssal peridotites are evidence for active communication between the Earth's hydrosphere and the upper mantle, where exchange and retention of both major and trace elements occur. Bulk rock Nd isotopes in serpentinized abyssal peridotites imply interaction of seawater with the peridotite. In contrast, the Nd isotopes of clinopyroxenes from serpentinized abyssal peridotites retain their primary magmatic signature. It is currently unclear if, how and where seawater-derived Nd and other REE are being added or exchanged with the mantle peridotite minerals during serpentinization. To remedy this knowledge gap, we present in situ trace and major element concentrations, bulk rock and sequential leaching experiment trace element concentrations as well as Nd, Sr isotope data on refertilized and depleted serpentinized abyssal peridotites from the Southwest Indian Ridge. The secondary serpentine matrix and magnetite veins in these peridotites have elevated LREE concentrations, with variable negative Ce anomalies and large Rb, Sr, Pb and U enrichments that resemble seawater trace element patterns. The LREE concentrations in the serpentine phase are higher than those expected for the primary mantle mineralogy (olivine, orthopyroxene) based on data from relic clinopyroxenes and equilibrium partition coefficients. These data are consistent with seawater-derived REE addition to the peridotite during serpentinization. The bulk rocks have more radiogenic Sr and more unradiogenic Nd isotopes than their clinopyroxene (up to 8 εNd units lower than clinopyroxene). Sequential leaching experiments designed to mobilize secondary carbonates and Fe-oxides show even more unradiogenic Nd isotope ratios in the leachates than the bulk rock and clinopyroxene, approaching seawater compositions (up to 15 εNd units lower than clinopyroxene). Mass balance calculations using trace elements or Nd isotopes suggest that up to 30% of the bulk peridotite Nd budget is of seawater origin and

  3. Investigating Rare Earth Element Systematics in the Marcellus Shale

    NASA Astrophysics Data System (ADS)

    Yang, J.; Torres, M. E.; Kim, J. H.; Verba, C.

    2014-12-01

    The lanthanide series of elements (the 14 rare earth elements, REEs) have similar chemical properties and respond to different chemical and physical processes in the natural environment by developing unique patterns in their concentration distribution when normalized to an average shale REE content. The interpretation of the REE content in a gas-bearing black shale deposited in a marine environment must therefore take into account the paleoredox conditions of deposition as well as any diagenetic remobilization and authigenic mineral formation. We analyzed 15 samples from a core of the Marcellus Shale (Whipkey ST1, Greene Co., PA) for REEs, TOC, gas-producing potential, trace metal content, and carbon isotopes of organic matter in order to determine the REE systematics of a black shale currently undergoing shale gas development. We also conducted a series of sequential leaching experiments targeting the phosphatic fractions in order to evaluate the dominant host phase of REEs in a black shale. Knowledge of the REE system in the Marcellus black shale will allow us to evaluate potential REE release and behavior during hydraulic fracturing operations. Total REE content of the Whipkey ST1 core ranged from 65-185 μg/g and we observed three distinct REE shale-normalized patterns: middle-REE enrichment (MREE/MREE* ~2) with heavy-REE enrichment (HREE/LREE ~1.8-2), flat patterns, and a linear enrichment towards the heavy-REE (HREE/LREE ~1.5-2.5). The MREE enrichment occurred in the high carbonate samples of the Stafford Member overlying the Marcellus Formation. The HREE enrichment occurred in the Union Springs Member of the Marcellus Formation, corresponding to a high TOC peak (TOC ~4.6-6.2 wt%) and moderate carbonate levels (CaCO3 ~4-53 wt%). Results from the sequential leaching experiments suggest that the dominant host of the REEs is the organic fraction of the black shale and that the detrital and authigenic fractions have characteristic MREE enrichments. We present our

  4. Attenuation of rare earth elements in a boreal estuary

    NASA Astrophysics Data System (ADS)

    Åström, Mats E.; Österholm, Peter; Gustafsson, Jon Petter; Nystrand, Miriam; Peltola, Pasi; Nordmyr, Linda; Boman, Anton

    2012-11-01

    This study focuses on attenuation of rare earth elements (REE) when a boreal creek, acidified and loaded with REE and other metals as a result of wetland drainage, empties into a brackish-water estuary (salinity < 6‰). Surface water was collected in a transect from the creek mouth to the outer estuary, and settling (particulate) material in sediment traps moored at selected locations in the estuary. Ultrafiltration, high-resolution ICP-MS and modeling were applied on the waters, and a variety of chemical reagents were used to extract metals from the settling material. Aluminium, Fe and REE transported by the acidic creek were extensively removed in the inner/central estuary where the acidic water was neutralised, whereas Mn was relatively persistent in solution and thus redistributed to particles and deposited further down the estuary. The REE removal was caused by several contemporary mechanisms: co-precipitation with oxyhydroxides (mainly Al but also Fe), complexation with flocculating humic substances and sorption to suspended particles. Down estuary the dissolved REE pool, remaining after removal, was fractionated: the <1 kDa pool became depleted in the middle REE and the colloidal (0.45 μm-1 kDa) pool depleted in the middle and heavy REE. This fractionation was controlled by the removal process, such that those REE with highest affinity for the settling particles became most depleted in the remaining dissolved pool. Modeling, based on Visual MINTEQ version 3.0 and the Stockholm Humic Model after revision and updating, predicted that the dissolved (<0.45 μm) REE pool in the estuary is bound almost entirely to humic substances. Acid sulphate soils, the source of the REE and other metals in the creek water, are widespread on coastal plains worldwide and therefore the REE attenuation patterns and mechanisms identified in the studied estuary are relevant for recognition of similar geochemical processes and conditions in a variety of coastal locations.

  5. Recovery and Separation of Rare Earth Elements Using Salmon Milt

    PubMed Central

    Takahashi, Yoshio; Kondo, Kazuhiro; Miyaji, Asami; Watanabe, Yusuke; Fan, Qiaohui; Honma, Tetsuo; Tanaka, Kazuya

    2014-01-01

    Recycling rare earth elements (REEs) used in advanced materials such as Nd magnets is important for the efficient use of REE resources when the supply of several REEs is limited. In this work, the feasibility of using salmon milt for REE recovery and separation was examined, along with the identification of the binding site of REEs in salmon milt. Results showed that (i) salmon milt has a sufficiently high affinity to adsorb REEs and (ii) the adsorption capacity of the milt is 1.04 mEq/g, which is comparable with that of commercial cation exchange resin. Heavier REEs have higher affinity for milt. A comparison of stability constants and adsorption patterns of REEs discussed in the literature suggests that the phosphate is responsible for the adsorption of REE in milt. The results were supported by dysprosium (Dy) and lutetium (Lu) LIII-edge extended x-ray absorption fine structure (EXAFS) spectroscopy. The REE-P shell was identified for the second neighboring atom, which shows the importance of the phosphate site as REE binding sites. The comparison of REE adsorption pattern and EXAFS results between the milt system and other adsorbent systems (cellulose phosphate, Ln-resin, bacteria, and DNA-filter hybrid) revealed that the coordination number of phosphate is correlated with the slope of the REE pattern. The separation column loaded with milt was tested to separate REE for the practical use of salmon milt for the recovery and separation of REE. However, water did not flow through the column possibly because of the hydrophobicity of the milt. Thus, sequential adsorption–desorption approach using a batch-type method was applied for the separation of REE. As an example of the practical applications of REE separation, Nd and Fe(III) were successfully separated from a synthetic solution of Nd magnet waste by a batch-type method using salmon milt. PMID:25490035

  6. Cosmic-ray abundances of the even charge elements from Sn-50 to Ce-58 measured on HEAO-3

    NASA Technical Reports Server (NTRS)

    Stone, E. C.; Garrard, T. L.; Krombel, K. E.; Binns, W. R.; Israel, M. H.; Klarmann, J.; Brewster, N. R.; Fickle, R. K.; Waddington, C. J.

    1983-01-01

    Elements with even atomic number (Z) in the interval Z = 50-58 have been resolved in the cosmic radiation using the Heavy Nuclei Experiment on the HEAO-3 satellite. The observation that Sn-50 and Ba-56 are more abundant than Te-52 and Xe-54 indicates a substantial s-process contribution to the cosmic ray source. A significant abundance of Ce-58 provides further support for this finding.

  7. Carbonatite and alkaline intrusion-related rare earth element deposits–A deposit model

    USGS Publications Warehouse

    Verplanck, Philip L.; Van Gosen, Bradley S.

    2011-01-01

    The rare earth elements are not as rare in nature as their name implies, but economic deposits with these elements are not common and few deposits have been large producers. In the past 25 years, demand for rare earth elements has increased dramatically because of their wide and diverse use in high-technology applications. Yet, presently the global production and supply of rare earth elements come from only a few sources. China produces more than 95 percent of the world's supply of rare earth elements. Because of China's decision to restrict exports of these elements, the price of rare earth elements has increased and industrial countries are concerned about supply shortages. As a result, understanding the distribution and origin of rare earth elements deposits, and identifying and quantifying our nation's rare earth elements resources have become priorities. Carbonatite and alkaline intrusive complexes, as well as their weathering products, are the primary sources of rare earth elements. The general mineral deposit model summarized here is part of an effort by the U.S. Geological Survey's Mineral Resources Program to update existing models and develop new descriptive mineral deposit models to supplement previously published models for use in mineral-resource and mineral-environmental assessments. Carbonatite and alkaline intrusion-related REE deposits are discussed together because of their spatial association, common enrichment in incompatible elements, and similarities in genesis. A wide variety of commodities have been exploited from carbonatites and alkaline igneous rocks, such as rare earth elements, niobium, phosphate, titanium, vermiculite, barite, fluorite, copper, calcite, and zirconium. Other enrichments include manganese, strontium, tantalum, thorium, vanadium, and uranium.

  8. Electrical transport mechanism in a newly synthesized rare earth double perovskite oxide Sr2CeTaO6

    NASA Astrophysics Data System (ADS)

    Bharti, Chandrahas; Chanda, Sadhan; Sinha, T. P.

    2013-01-01

    A rare earth double perovskite oxide strontium cerium tantalate, Sr2CeTaO6 (SCT) is synthesized by the solid state reaction technique for the first time. The determination of lattice parameters and the identification of phase are carried out by the Rietveld refinement method (RRM) using the Fullprof program in the space group P21/n (C52h). A structure of SCT is obtained from RRM. The bond angle and bond length are calculated and listed in Table 1 for SCT. A small amount of impurity of CeO2 is found in the refinement with space group Fm3m. The scanning electron micrograph shows the average grain size ∼2 μm. The ac electrical property is investigated in the temperature range from 303 to 703 K and in the frequency range from 0.1 kHz to 1 MHz using impedance spectroscopy. The relaxation mechanism of SCT is explained in detail by fitting experimental impedance and electric modulus data with the modified Debye (Cole-Cole) model. The frequency-dependent electrical data are analyzed in the framework of the conductivity and modulus formalisms. The σac data are fitted with Jonscher's universal power law. The dc conductivity (σdc) (calculated from σac) follows an Arrhenius law with the estimated conduction activation energy =0.78 eV. The scaling behavior of imaginary part of electrical impedance (Z″) shows that the relaxation describes the same mechanism at various temperatures.

  9. Rare-earth elements in the Permian Phosphoria Formation: Paleo proxies of ocean geochemistry

    USGS Publications Warehouse

    Piper, D.Z.; Perkins, R.B.; Rowe, H.D.

    2007-01-01

    The geochemistry of deposition of the Meade Peak Member of the Phosphoria Formation (MPM) in southeast Idaho, USA, a world-class sedimentary phosphate deposit of Permian age that extends over 300,000 km2, is ascertained from its rare earth element (REE) composition. Ratios of REE:Al2O3 suggest two sources-seawater and terrigenous debris. The seawater-derived marine fraction identifies bottom water in the Phosphoria Sea as O2-depleted, denitrifying (suboxic) most of the time, and seldom sulfate-reducing (anoxic). This interpretation is supported by earlier research that showed progressively greater ratios in the marine sediment fraction of Cr:Ni>V:Ni???Mo:Ni, relative to their ratios in seawater; for which marine Cr, V, and Mo can have a dominantly O2-depleted bottom-water source and Ni a photic-zone, largely algal, source. The water chemistry was maintained by a balance between bacterial oxidation of organic matter settling through the water column, determined largely by primary productivity in the photic zone, and the flux of oxidants into the bottom water via advection of seawater from the open ocean. Samples strongly enriched in carbonate fluorapatite, the dominant REE host mineral, have variable Er/Sm, Tm/Sm, and Yb/Sm ratios. Their distribution may represent greater advection of seawater between the Phosphoria Sea and open ocean during deposition of two ore zones than a center waste and greater upwelling of nutrient-enriched water into the photic zone. However, the mean rate of deposition of marine Ni, a trace nutrient of algae, and PO43-, a limiting nutrient, indicate that primary productivity was probably high throughout the depositional history. An alternative interpretation of the variable enrichments of Er, Tm, and Yb, relative to Sm, is that they may reflect temporally variable carbonate alkalinity of open-ocean seawater in Permian time. A more strongly negative Ce anomaly for all phosphatic units than the Ce anomaly of modern pelletal phosphate is

  10. Rare earth and trace elements of fossil vertebrate bioapatite as palaeoenvironmental and sedimentological proxies

    NASA Astrophysics Data System (ADS)

    Žigaitė, Živilė; Fadel, Alexandre; Pérez-Huerta, Alberto; Jeffries, Teresa

    2015-04-01

    Rare earth (REE) and trace element compositions of fossil vertebrate dental microremains have been studied in Silurian and Devonian vertebrate dental scales and spines in-situ, using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Samples were selected from the well-known Silurian bone beds of Vesiku and Ohesaare in Saaremaa island of Estonia, and a number of Lower Devonian localities from Spitsbergen (Svalbard), Andrée Land group. Biomineral preservation was assessed using spot semi-quantitative elemental chemistry (SEM-EDS) and electron back-scatter difractometry (EBSD) for cristallinity imaging. The obtained PAAS shale-normalised REE concentrations were evaluated using basic geochemical calculations and quantifications. The REE patterns from the Lower Devonian vertebrate apatite from Andrée Land, Spitsbergen (Wood Bay and Grey Hœk formations) did not show any recognisable taxon-specific behavior, but had rather well expressed differences of REE compositions related to biomineral structure and sedimentary settings, suggesting REE instead to reflect burial environments and sedimentological history. The Eu anomaly recorded in two of the studied localities but not in the other indicate different taphonomic conditions and palaeoenvironment, while La/Sm, La/Yb ratios sugeest considerable influence of terrestrial freshwater during the early diagenesis. The La/Yb and La/Sm plots also agree with the average REE concentrations, reflecting domination of the adsoption over substitution as principal REE uptake mechanism in the fossils which had significantly lower overall REE concentrations, and vice versa. Vesiku (Homerian, Wenlock) microremains yielded very uniform REE patterns with slightly lower overall REE concentrations in enameloid than in dentine, with strong enrichment in middle REE and depletion in heavy REE. Negative Europium (Eu) anomaly was pronounced in all the profiles, but Cerium (Ce) anomalies were not detected suggesting possible

  11. PROCESS FOR SEPARATING AMERICIUM AND CURIUM FROM RARE EARTH ELEMENTS

    DOEpatents

    Baybarz, R.D.; Lloyd, M.H.

    1963-02-26

    This invention relates to methods of separating americium and curium values from rare earth values. In accordance with the invention americium, curium, and rare earth values are sorbed on an anion exchange resin. A major portion of the rare earth values are selectively stripped from the resin with a concentrated aqueous solution of lithium chloride, and americium, curium, and a minor portion of rare earth values are then stripped from the resin with a dilute aqueous solution of lithium chloride. The americium and curium values are further purified by increasing the concentration of lithium chloride in the solution to at least 8 molar and selectively extracting rare earth values from the resulting solution with a monoalkylphosphoric acid. (AEC)

  12. Core-Mantle Partitioning of Volatile Siderophile Elements and the Origin of Volatile Elements in the Earth

    NASA Technical Reports Server (NTRS)

    Nickodem, K.; Righter, K.; Danielson, L.; Pando, K.; Lee, C.

    2012-01-01

    There are currently several hypotheses on the origin of volatile siderophile elements in the Earth. One hypothesis is that they were added during Earth s accretion and core formation and mobilized into the metallic core [1], others claim multiple stage origin [2], while some hypothesize that volatiles were added after the core already formed [3]. Several volatile siderophile elements are depleted in Earth s mantle relative to the chondrites, something which continues to puzzle many scientists. This depletion is likely due to a combination of volatility and core formation. The Earth s core is composed of Fe and some lighter constituents, although the abundances of these lighter elements are unknown [4]. Si is one of these potential light elements [5] although few studies have analyzed the effect of Si on metal-silicate partitioning, in particular the volatile elements. As, In, Ge, and Sb are trace volatile siderophile elements which are depleted in the mantle but have yet to be extensively studied. The metal-silicate partition coefficients of these elements will be measured to determine the effect of Si. Partition coefficients depend on temperature, pressure, oxygen fugacity, and metal and silicate composition and can constrain the concentrations of volatile, siderophile elements found in the mantle. Reported here are the results from 13 experiments examining the partitioning of As, In, Ge, and Sb between metallic and silicate liquid. These experiments will examine the effect of temperature, and metal-composition (i.e., Si content) on these elements in or-der to gain a greater understanding of the core-mantle separation which occurred during the Earth s early stages. The data can then be applied to the origin of volatile elements in the Earth.

  13. Infrared and visible emissions of rare-earth-doped CeO2 phosphor.

    PubMed

    Chandrakar, D; Kaur, J; Dubey, V; Suryanarayana, N S; Parganiha, Y

    2015-12-01

    This paper reports the synthesis and characterization of Er(3+)-doped CeO2 phosphor with variable concentrations of erbium. The sample was synthesized using a solid-state reaction method, which is useful for the large-scale production of phosphors and is also eco-friendly. The prepared sample was characterized using an X-ray diffraction (XRD) technique. The XRD pattern confirmed that sample has the pure cubic fluorite crystal structure of CeO2. The crystallite size of the prepared phosphor was determined by Scherer's formula and the crystallite size giving an intense XRD peak is 40.06 nm. The surface morphology of the phosphor was determined by field emission gun scanning electron microscopy (FEGSEM). From the FEGSEM image, good surface morphology with some agglomerates was found. The functional group in the prepared sample was analysed by Fourier transform infrared (FTIR) spectroscopy. All samples prepared with variable concentrations of Er(3+) (0.1-2 mol%) were studied by photoluminescence analysis and it was found that the excitation spectra of the prepared phosphor shows broad excitation centred at 251 nm. Emission spectra at different concentrations of Er(3+) show strong peaks at 413 and 470 nm and a weaker peak at 594 nm. The dominant peaks at 413 and 470 nm are caused by the allowed electronic transition (4)S3/2 → (4)I15/2 and the weaker transition at 594 nm is due to the transition (4)F9/2 → (4)I15/2. Spectrophotometric determinations of peaks were evaluated using the Commission Internationale de I'Eclairage (CIE) technique. The emission spectra were also observed using an infrared (IR) laser 980 nm source, and three distinct peaks were found in the IR region at 848, 870 and 980 nm. The prepared phosphor has utility for application in display devices. PMID:25810371

  14. Photon management properties of rare-earth (Nd,Yb,Sm)-doped CeO2 films prepared by pulsed laser deposition.

    PubMed

    Balestrieri, Matteo; Colis, Silviu; Gallart, Mathieu; Schmerber, Guy; Bazylewski, Paul; Chang, Gap Soo; Ziegler, Marc; Gilliot, Pierre; Slaoui, Abdelilah; Dinia, Aziz

    2016-01-28

    CeO2 is a promising material for applications in optoelectronics and photovoltaics due to its large band gap and values of the refractive index and lattice parameters, which are suitable for silicon-based devices. In this study, we show that trivalent Sm, Nd and Yb ions can be successfully inserted and optically activated in CeO2 films grown at a relatively low deposition temperature (400 °C), which is compatible with inorganic photovoltaics. CeO2 thin films can therefore be efficiently functionalized with photon-management properties by doping with trivalent rare earth (RE) ions. Structural and optical analyses provide details of the electronic level structure of the films and of their energy transfer mechanisms. In particular, we give evidence of the existence of an absorption band centered at 350 nm from which energy transfer to rare earth ions occurs. The transfer mechanisms can be completely explained only by considering the spontaneous migration of Ce(3+) ions in CeO2 at a short distance from the RE(3+) ions. The strong absorption cross section of the f-d transitions in Ce(3+) ions efficiently intercepts the UV photons of the solar spectrum and therefore strongly increases the potential of these layers as downshifters and downconverters. PMID:26699802

  15. Origin and Dynamics of Rare Earth Elements during Flood Events in Contaminated River Basins: Sr-Nd-Pb Isotopic Evidence.

    PubMed

    Hissler, Christophe; Stille, Peter; Iffly, Jean François; Guignard, Cédric; Chabaux, François; Pfister, Laurent

    2016-05-01

    In order to precisely quantify the contribution of anthropogenic activities and geogenic sources to the dissolved and suspended loads of rivers we have combined for the first time Rare Earth Element (REE) concentrations with Sr-Nd-Pb isotope ratios. We observed enrichments in Anthropogenic Rare Earth Elements (AREE) for dissolved (Gd) and suspended (Ce and Nd) loads of river water. During flood events, AREE anomalies progressively disappeared and gave way to the geogenic chemical signature of the basin in both dissolved and suspended loads. The isotopic data confirm these observations and shed new light on the trace elements sources. On the one hand, dissolved loads have peculiar isotopic characteristics and carry mainly limestone-derived and anthropogenic Sr and Nd as well as significant amounts of anthropogenic Pb. On the other hand, the results clearly indicate that anthropogenic contributions impact the suspended loads in all hydrological conditions. This study demonstrates that anthropogenic contributions to the river may change not only Pb but also Sr and Nd isotopic compositions in both dissolved and suspended loads. This is of importance for future provenance studies. PMID:27045616

  16. Rare Earth elements as sediment tracers in Mangrove ecosystems

    NASA Astrophysics Data System (ADS)

    Ramanathan, A. L.; Swathi, S.

    2013-05-01

    Rare earth elements have been widely used as geochemical source fingerprints of rocks and sediments to study processes involving cosmo-chemistry, igneous petrology, tectonic setting and for investigations of water-rock interactions and weathering processes including transport of weathering products to the oceans.Many studies have addressed the use of REEs in investigating the environmental impact of human activity and demonstrated that the REE natural distribution in sediment from densely industrialised and populated regions can be altered by anthropogenic influences.The coastal wetlands like Mangroves are ultimate sinks for all the material derived from the terrestrial and marine environment.The high productivity and low ratio of sediment respiration to net primary production gives mangrove sediments the potential for long-term sequestration of these pollutants/metals before reaching the coastal ocean. Geochemical study of REE in these sedimentary systems is useful for determining the nature of the biogeochemical processes. In particular, REE show a great sensitivity to pH changes, redox conditions and adsorption/ desorption reactions. So, they may be used as markers of discharge provenance, weathering processes, changes in environmental conditions in the water and sediments of Mangrove/wetland systems. Our study aims to establish the abundance, distribution and enrichment of REEs to track the sediment sources and biogeochemical processes occurring in the mangrove environment.Core sediments were collected from the different environmental settings within the Pichavaram mangrove area.Higher REE concentration in Pichavaram sediments indicated greater input from sources like terrestrial weathering and anthropogenic activities which in turn are affected by saline mixing and dynamic physico-chemical processes occurring in the mangrove environment. REE enrichment order was attributed to the alkaline pH (7-8.5) and reducing conditions prevailing in the mangrove

  17. Evolution of the atomic order and valence state of rare-earth atoms and uranium in a new carbon-metal composite—diphthalocyanine pyrolysate C64H32N16 Me ( Me = Y, La, Ce, Eu, and U)

    NASA Astrophysics Data System (ADS)

    Sovestnov, A. E.; Kapustin, V. K.; Tikhonov, V. I.; Fomin, E. V.; Chernenkov, Yu. P.

    2014-08-01

    The structure of a metal-carbon composite formed by the pyrolysis of diphthalocyanine of some rare-earth elements (Y, La, Ce, Eu) and uranium in the temperature range T ann = 800-1700°C has been investigated for the first time by the methods of X-ray diffraction analysis and X-ray line shift. It has been shown that, in the general case, the studied pyrolysates consist of three phases. One phase corresponds to the structure of graphite. The second phase corresponds to nitrides, carbides, and oxides of basic metal elements with a crystallite size ranging from 5 to 100 nm. The third phase is amorphous or consisting of crystallites with a size of ˜1 nm. It has been found that all the basic elements (Y, La, Ce, Eu, U) and incorporated iodine atoms in the third phase are in a chemically bound state. The previously unobserved electronic configurations have been revealed for europium. The possibility of including not only atoms of elements forming diphthalocyanine but also other elements (for example, iodine) in the composite structure is of interest, in particular, for the creation of a thermally, chemically, and radiation resistant metal-carbon matrix for the radioactive waste storage.

  18. Separation of rare earth elements by zone recrystallization

    NASA Astrophysics Data System (ADS)

    Akimov, D. V.; Dyachenko, A. N.; Egorov, N. B.; Zhuravlev, N. A.

    2016-01-01

    The separation of holmium and cerium by zone recrystallization using a mixture of HoCl3·6H2O and CeCl3·6H2O was investigated. It is shown that holmium is enriched at the end of the crystal that the recrystallization zone moves to, while cerium is concentrated in the primary solidification zone. The possible reasons for the experimentally observed distribution of hydrated ions of cerium and holmium along the length of the ingot are discussed. Also the coefficients of enrichment and separation are calculated.

  19. Earth's moderately volatile element composition may not be chondritic: Evidence from In, Cd and Zn

    NASA Astrophysics Data System (ADS)

    Wang, Zaicong; Laurenz, Vera; Petitgirard, Sylvain; Becker, Harry

    2016-02-01

    Current models assume that siderophile volatile elements (SVE) are depleted in bulk Earth to the same extent as lithophile elements of similar volatility. The observed additional depletion of many SVE relative to lithophile elements in the bulk silicate Earth (BSE) is ascribed to partitioning of SVE into Earth's core. However, the assumption of similar volatility of moderately volatile elements during Earth formation processes as in solar gas is quite uncertain. Here, these assumptions will be tested by assessing abundances and ratios of indium and cadmium in the BSE using new data on mantle rocks, and the application of high- and low-pressure-temperature metal-silicate partitioning data. New bulk rock abundance data of In and Cd obtained on bulk rocks of peridotite tectonites and xenoliths by isotope dilution refine previous results inferred from basalts and in-situ analyses of silicate minerals in peridotite xenoliths. The CI chondrite-normalized abundance of In in the BSE is similar to zinc and is 3-4 times higher than Cd. New and published low- and high-P-T metal-silicate partitioning data indicate that, during core formation at a range of conditions, In is always more siderophile than Zn and Cd. Adding the fraction of these elements in Earth's core to the BSE results in bulk Earth compositions that yield higher CI chondrite normalized abundances of In in the bulk Earth compared to Zn and Cd. Because In is more volatile than Zn and Cd in gas of solar composition, suprachondritic In/Zn and In/Cd in the bulk Earth suggest that during formation of Earth or its building materials, the volatilities of these elements and perhaps other volatile elements likely have changed significantly (i.e. In became less volatile). The results also suggest that known carbonaceous chondrites likely did not deliver the main volatile element-rich fraction of the Earth. Various arguments suggest that the loss of moderately volatile elements during planetary accretion should be limited

  20. RARE EARTH ELEMENTS: A REVIEW OF PRODUCTION, PROCESSING, RECYCLING, AND ASSOCIATED ENVIRONMENTAL ISSUES

    EPA Science Inventory

    Rare earth elements (REEs) are a group of 15 chemical elements in the periodic table, specifically the lanthanides. Two other elements, scandium and yttrium, have a similar physiochemistry to the lanthanides, are commonly found in the same mineral assemblages, and are often refe...

  1. Fractionation of rare-earth elements in allanite and monazite as related to geology of the Mt. Wheeler mine area, Nevada

    USGS Publications Warehouse

    Lee, D.E.; Bastron, H.

    1967-01-01

    Rare-earth contents of 20 allanites and 13 monazites, accessory minerals from a restricted outcrop area of intrusive granitic rocks, are reported. A quantity called sigma (??), which is the sum of the atomic percentages of La, Ce and Pr, is used as an index of composition with respect to the rare-earth elements. Values of sigma vary from 61.3 to 80.9 at.% for these allanites and monazites, representing an appreciable range of composition in terms of the rare-earth elements. Degree of fractionation of rare earths varies directly with CaO content of the granitic rocks, which in turn depends largely on proximity of limestone. Four xenoliths included in the study suggest that spotty mosaic equilibria are superimposed on the regional gradients and that locally the degree of fractionation of rare earths responds to whole rock composition over distances of a few yards or less. The chemistry of the granitic rocks under study appears to be similar in some respects to that of alkalio rocks and carbonatites. Allanites from the most calcium-rich rocks show a pronounced concentration of the most basic rare earths, and whole-rock concentrations of such rare constituents as total cerium earths, Zr, F, Ti, Ba and Sr increase sympathetically with whole-rock calcium. The explanation for the concentration gradients observed in this chemical system must involve assimilation more than magmatic differentiation. ?? 1967.

  2. Rare Earth Elements: A Tool for Understanding the Behaviour of Trivalent Actinides in the Geosphere

    SciTech Connect

    Buil, Belen; Gomez, Paloma; Garralon, Antonio; Turrero, M. Jesus

    2007-07-01

    Rare earth element (REE) concentrations have been determined in groundwaters, granite and fracture fillings in a restored uranium mine. The granitoids normalized REE patterns of groundwaters show heavy rare earth elements (HREE)-enrichment and positive Eu anomalies. This suggests that the REE are fractionated during leaching from the source rocks by groundwaters. Preferential leaching of HREE would be consistent with the greater stability of their aqueous complexes compared to those of the light rare earth elements (LREE), together with the dissolution of certain fracture filling minerals, dissolution/alteration of phyllosilicates and colloidal transport. (authors)

  3. Ce53Fe12S90X3 (X = Cl, Br, I): the first rare-earth transition-metal sulfide halides.

    PubMed

    Mills, Allison M; Ruck, Michael

    2006-06-26

    The compounds Ce53Fe12S90X3 (X = Cl, Br, I), which represent the first examples of rare-earth transition-metal sulfide halides, were prepared using the reactive-flux method, through reaction of Ce2S3, FeS, or Fe and S in a CeX3 flux at 1320 K. Their structures were determined by single-crystal X-ray diffraction. The compounds are isostructural, crystallizing in the trigonal space group Rm with Z = 1 [Ce53Fe12S90Cl3, a = 13.9094(9) A, c = 21.604(2) A, V = 3619.7(4) A3; Ce(53)Fe(12)S(90)Br(3), a = 13.916(1) A, c = 21.824(2) A, V = 3660.0(5) A3; Ce53Fe12S90I3, a = 13.863(3) A, c = 21.944(6) A, V = 3652(2) A3]. The structure adopted is a stuffed variant of the La52Fe12S90 structure type. Fe2S9 dimers of face-sharing octahedra are linked by face- and vertex-sharing capped CeS6 trigonal prisms, forming a three-dimensional framework containing cuboctahedral cavities of two sizes. The smaller cavities accommodate alternative sites for disordered cerium atoms. The larger cavities, which remain empty in the parent structure, are filled by halogen atoms in Ce53Fe12S90X3. Alternatively, the structure can be described as a 9-fold superstructure of the Mn5Si3 structure type (P6(3)/mcm), with a = a' and c = 3c'. Temperature-dependent magnetic susceptibility measurements suggest that Ce53Fe12S90I3 may order antiferromagnetically at low temperatures. PMID:16780341

  4. Rare earth elements and neodymium isotopes in sedimentary organic matter

    NASA Astrophysics Data System (ADS)

    Freslon, Nicolas; Bayon, Germain; Toucanne, Samuel; Bermell, Sylvain; Bollinger, Claire; Chéron, Sandrine; Etoubleau, Joel; Germain, Yoan; Khripounoff, Alexis; Ponzevera, Emmanuel; Rouget, Marie-Laure

    2014-09-01

    We report rare earth element (REE) and neodymium (Nd) isotope data for the organic fraction of sediments collected from various depositional environments, i.e. rivers (n = 25), estuaries (n = 18), open-ocean settings (n = 15), and cold seeps (n = 12). Sedimentary organic matter (SOM) was extracted using a mixed hydrogen peroxide/nitric acid solution (20%-H2O2-0.02 M-HNO3), after removal of carbonate and oxy-hydroxide phases with dilute hydrochloric acid (0.25 M-HCl). A series of experimental tests indicate that extraction of sedimentary organic compounds using H2O2 may be complicated occasionally by partial dissolution of sulphide minerals and residual carbonates. However, this contamination is expected to be minor for REE because measured concentrations in H2O2 leachates are about two-orders of magnitude higher than in the above mentioned phases. The mean REE concentrations determined in the H2O2 leachates for samples from rivers, estuaries, coastal seas and open-ocean settings yield relatively similar levels, with ΣREE = 109 ± 86 ppm (mean ± s; n = 58). The organic fractions leached from cold seep sediments display even higher concentration levels (285 ± 150 ppm; mean ± s; n = 12). The H2O2 leachates for most sediments exhibit remarkably similar shale-normalized REE patterns, all characterized by a mid-REE enrichment compared to the other REE. This suggests that the distribution of REE in leached sedimentary organic phases is controlled primarily by biogeochemical processes, rather than by the composition of the source from which they derive (e.g. pore, river or sea-water). The Nd isotopic compositions for organic phases leached from river sediments are very similar to those for the corresponding detrital fractions. In contrast, the SOM extracted from marine sediments display εNd values that typically range between the εNd signatures for terrestrial organic matter (inferred from the analysis of the sedimentary detrital fractions) and marine organic matter

  5. Comparison of the partitioning behaviours of yttrium, rare earth elements, and titanium between hydrogenetic marine ferromanganese crusts and seawater

    USGS Publications Warehouse

    Bau, M.; Koschinsky, A.; Dulski, P.; Hein, J.R.

    1996-01-01

    In order to evaluate details of the partitioning behaviours of Y, rare earth elements (REEs), and Ti between inorganic metal oxide surfaces and seawater, we studied the distribution of these elements in hydrogenetic marine ferromanganese (Fe-Mn) crusts from the Central Pacific Ocean. Nonphosphatized Fe-Mn crusts display shale-normalized rare earths and yttrium (REYSN) patterns (Y inserted between Dy and Ho) that are depleted in light REEs (LREEs) and which show negative anomalies for YSN, and positive anomalies for LaSN, EuSN, GdSN, and in most cases, CeSN. They show considerably smaller Y/ Ho ratios than seawater or common igneous and clastic rocks, indicating that Y and Ho are fractionated in the marine environment. Compared to P-poor crusts, REYSN patterns of phosphatized Fe-Mn crusts are similar, but yield pronounced positive YSN anomalies, stronger positive LaSN anomalies, and enrichment of the HREEs relative to the MREEs. The data suggest modification of REY during phosphatization and indicate that studies requiring primary REY distributions or isotopic ratios should be restricted to nonphosphatized (layers of) Fe-Mn crusts. Apparent bulk coefficients, KMD, describing trace metal partitioning between nonphosphatized hydrogenetic Fe-Mn crusts and seawater, are similar for Pr to Eu and decrease for Eu to Yb. Exceptionally high values of KCeD, which are similar to those of Ti, result from oxidative scavenging of Ce and support previous suggestions that Ce(IV) is a hydroxide-dominated element in seawater. Yttrium and Gd show lower KD values than their respective neighbours in the REY series. Results of modelling the exchange equilibrium between REY dissolved in seawater and REY sorbed on hydrous Fe-Mn oxides corroborate previous studies that suggested the surface complexation of REY can be approximated by their first hydroxide binding constant. Negative "anomalies" occur for stabilities of bulk surface complexes of Gd, La, and particularly Y. The differences in

  6. Effect of earthworms (Eisenia fetida) on the fractionation and bioavailability of rare earth elements in nine Chinese soils.

    PubMed

    Wen, Bei; Liu, Ying; Hu, Xiao-yu; Shan, Xiao-quan

    2006-05-01

    The effect of earthworm (Eisenia fetida) activity on soil pH, dissolved organic carbon (DOC), fraction distribution pattern and bioavailability of rare earth elements (REEs) Y, La, Ce, Pr and Nd in nine Chinese soils were investigated using pot experiments. A three-step extraction procedure recommended by the European Community (Standards, Measurements and Testing Programme) was used to fractionate REEs in soils into water soluble, exchangeable and carbonate bound (B1), Fe- and Mn-oxides bound (B2) and organic matter and sulfide bound (B3). Inoculated with earthworms, the soil pH, DOC and water-soluble rare earth elements fraction increased. A significant correlation was obtained between the increased DOC and the increased water-soluble REEs. REEs in fraction B1 increased after earthworm inoculation, while those in fraction B3 decreased. No significant differences were observed for REEs in fraction B2. The biomass and the concentrations of REEs in wheat shoots and roots increased after the treatment with earthworms. The results demonstrated that earthworm activity increased the mobility and bioavailability of REEs in soils. PMID:16289225

  7. Effects of supplementing rare earth element cerium on rumen fermentation, nutrient digestibility, nitrogen balance and plasma biochemical parameters in beef cattle.

    PubMed

    Lin, S X; Wei, C; Zhao, G Y; Zhang, T T; Yang, K

    2015-12-01

    The objectives of the trial were to investigate the effects of supplementing rare earth element (REE) cerium (Ce) on rumen fermentation, nutrient digestibility, methane (CH4 ) production, nitrogen (N) balance and plasma biochemical parameters in beef cattle. Four Simmental male cattle, aged at 14 months, with initial liveweight of 355 ± 8 kg and fitted with permanent rumen cannulas, were used as experimental animals. The cattle were fed with a total mixed ration (TMR) composed of concentrate mixture and corn silage. Four levels of cerium chloride (CeCl3 ·7H2 O, purity 99.9%), that is 0, 80, 160 and 240 mg CeCl3 /kg DM, were added to basal ration in a 4 × 4 Latin square design. Each experimental period lasted 15 days, of which the first 12 days were for pre-treatment and the last 3 days were for sampling. The results showed that supplementing CeCl3 at 160 or 240 mg/kg DM increased neutral detergent fibre (NDF) digestibility (p < 0.05) and tended to increased acid detergent fibre (ADF) digestibility (p = 0.083). Supplementing CeCl3 at 80, 160 or 240 mg/kg DM decreased the molar ratio of rumen acetate to propionate linearly (p < 0.05). Supplementing CeCl3 at 160 or 240 mg/kg DM decreased total N excretion, urinary N excretion and increased N retention (p < 0.05), increased excretion of total urinary purine derivatives (PD) (p < 0.05) and decreased CH4 /kg DMI (p < 0.05). In conclusion, supplementing CeCl3 at 160 or 240 mg/kg DM in the ration of beef cattle increased the digestibility of NDF, decreased the molar ratio of rumen acetate to propionate, increased N retention and microbial N flow and decreased CH4 /kg DMI. PMID:25787979

  8. Rare earth element concentrations in geological and synthetic samples using synchrotron X-ray fluorescence analysis

    USGS Publications Warehouse

    Chen, J.R.; Chao, E.C.T.; Back, J.M.; Minkin, J.A.; Rivers, M.L.; Sutton, S.R.; Cygan, G.L.; Grossman, J.N.; Reed, M.J.

    1993-01-01

    The concentrations of rare earth elements (REEs) in specific mineral grains from the Bayan Obo ore deposit and synthetic high-silica glass samples have been measured by synchrotron X-ray fluorescence (SXRF) analysis using excitation of the REE K lines between 33 and 63 keV. Because SXRF, a nondestructive analytical technique, has much lower minimum detection limits (MDLs) for REEs, it is an important device that extends the in situ analytical capability of electron probe microanalysis (EPMA). The distribution of trace amounts of REEs in common rock-forming minerals, as well as in REE minerals and minerals having minor quantities of REEs, can be analyzed with SXRF. Synchrotron radiation from a bending magnet and a wiggler source at the National Synchrotron Light Source, Brookhaven National Laboratory, was used to excite the REEs. MDLs of 6 ppm (La) to 26 ppm (Lu) for 3600 s in 60-??m-thick standard samples were obtained with a 25-??m diameter wiggler beam. The MDLs for the light REEs were a factor of 10-20 lower than the MDLs obtained with a bending magnet beam. The SXRF REE concentrations in mineral grains greater than 25 ??m compared favorably with measurements using EPMA. Because EPMA offered REE MDLs as low as several hundred ppm, the comparison was limited to the abundant light REEs (La, Ce, Pr, Nd). For trace values of medium and heavy REEs, the SXRF concentrations were in good agreement with measurements using instrumental neutron activation analysis (INAA), a bulk analysis technique. ?? 1993.

  9. The geochemistry of rare earth elements in groundwater from the Carnmenellis area, southwest England

    SciTech Connect

    Smedley, P.L. )

    1991-10-01

    Shallow groundwater samples from the Carnmenellis area of southwest England collected from wells, boreholes, springs, adits and stream baseflow represent recently recharged waters of low salinity. Their major ion concentrations closely reflect the lithology of their host rocks which comprise the Carnmenellis granite and Devonian metasediments (and metabasite) of greenschist grade. Groundwaters from the granite are predominantly Na-Cl or Na-Ca-Cl type while those from the metasediment are Na-Ca-Mg-Cl-HCO{sub 3} waters with a larger range of compositions. The major ion compositions are predominantly a function of water-rock interaction processes and the larger range of metasediment-water compositions probably reflects the greater lithological variation. Rare earth element (REE) concentrations of 0.45 {mu}m-filtered groundwater samples have been determined by inductively coupled plasma mass spectrometry (ICP-MS). A large range of concentrations exists and many are below detection limits but levels reach up to 229 {mu}g/1 (1.6 {mu}m) total REEs. The REEs are strongly controlled by pH with higher levels in groundwaters of pH < 6. In the granite, the REEs are probably derived mainly from the accessory minerals monazite and apatite as well as the high-REE framework minerals biotite and muscovite. The source of REEs in groundwater from the metasediments is more uncertain but probably includes clay minerals, chlorite, and carbonate. The observed REE compositions of granite- and metasediment-derived groundwaters from the Carnmenellis area are so distinctive that the REEs in general and Ce in particular might be useful as future tracers in studies of water-rock interaction and groundwater provenance.

  10. Geochemistry of some rare earth elements in groundwater, Vierlingsbeek, The Netherlands.

    PubMed

    Janssen, René P T; Verweij, Wilko

    2003-03-01

    Groundwater samples were taken from seven bore holes at depths ranging from 2 to 41m nearby drinking water pumping station Vierlingsbeek, The Netherlands and analysed for Y, La, Ce, Pr, Nd, Sm and Eu. Shale-normalized patterns were generally flat and showed that the observed rare earth elements (REE) were probably of natural origin. In the shallow groundwaters the REEs were light REE (LREE) enriched, probably caused by binding of LREEs to colloids. To improve understanding of the behaviour of the REE, two approaches were used: calculations of the speciation and a statistical approach. For the speciation calculations, complexation and precipitation reactions including inorganic and dissolved organic carbon (DOC) compounds, were taken into account. The REE speciation showed REE(3+), REE(SO(4))(+), REE(CO(3))(+) and REE(DOC) being the major species. Dissolution of pure REE precipitates and REE-enriched solid phases did not account for the observed REEs in groundwater. Regulation of REE concentrations by adsorption-desorption processes to Fe(III)(OH)(3) and Al(OH)(3) minerals, which were calculated to be present in nearly all groundwaters, is a probable explanation. The statistical approach (multiple linear regression) showed that pH is by far the most significant groundwater characteristic which contributes to the variation in REE concentrations. Also DOC, SO(4), Fe and Al contributed significantly, although to a much lesser extent, to the variation in REE concentrations. This is in line with the calculated REE-species in solution and REE-adsorption to iron and aluminium (hydr)oxides. Regression equations including only pH, were derived to predict REE concentrations in groundwater. External validation showed that these regression equations were reasonably successful to predict REE concentrations of groundwater of another drinking water pumping station in quite different region of The Netherlands. PMID:12598196

  11. Core-Mantle Partitioning of Volatile Elements and the Origin of Volatile Elements in Earth and Moon

    NASA Technical Reports Server (NTRS)

    Righter, Kevin; Pando, K.; Danielson, L.; Nickodem, K.

    2014-01-01

    Depletions of volatile siderophile elements (VSE; Ga, Ge, In, As, Sb, Sn, Bi, Zn, Cu, Cd) in mantles of Earth and Moon, constrain the origin of volatile elements in these bodies, and the overall depletion of volatile elements in Moon relative to Earth. A satisfactory explanation has remained elusive [1,2]. We examine the depletions of VSE in Earth and Moon and quantify the amount of depletion due to core formation and volatility of potential building blocks. We calculate the composition of the Earth's PUM during continuous accretion scenarios with constant and variable fO2. Results suggest that the VSE can be explained by a rather simple scenario of continuous accretion leading to a high PT metal-silicate equilibrium scenario that establishes the siderophile element content of Earth's PUM near the end of accretion [3]. Core formation models for the Moon explain most VSE, but calculated contents of In, Sn, and Zn (all with Tc < 750 K) are all still too high after core formation, and must therefore require an additional process to explain the depletions in the lunar mantle. We discuss possible processes including magmatic degassing, evaporation, condensation, and vapor-liquid fractionation in the lunar disk.

  12. Characterization of the rare earth orthophosphates and Ce-doped LaPO{sub 4} by X-ray Absorption Spectroscopy

    SciTech Connect

    Shuh, D.K.; Perry, D.; Terminello, L.J.; Boatner, L.A.; Abraham, M.M.

    1993-12-31

    X-ray Absorption Spectroscopy (XAS) of the Rare Earth (RE) 3d levels yields sharp peaks near the edges as a result of strong, quasi-atomic 3d{sup 10}4f {yields} 3d{sup 9}4f{sup n+1} (M{sub 4,5}) transitions that contain a wealth of spectroscopic features. XAS is a useful technique for the characterization of 4f-occupancy, 4f-hybridization, and valence in RE-containing materials. The XAS measurements of the single crystal RE-orthophosphates, as well as a range of Cedoped ({approx}1--30%) LaPO{sub 4} hosts were performed at the 3d edge in the total electron yield mode at beamline 8-2 at the Stanford Synchrotron Radiation Laboratory (SSRL). The XAS spectra of the RE ions in the orthophosphate matrix generally resemble that of the corresponding RE metal and emphasize the major contribution of the trivalent state to the electronic transitions occurring at the 3d edge. There is no energy shift of the La and Ce absorption peaks with Ce doping and furthermore, no additional transitions are observed in either spectral region. However, accompanying the Ce doping there is a significant narrowing of the La absorption peak full width half maximum that contrasts to the Ce features that exhibit no contraction. The La and Ce spectra indicate that the Ce-doping of LaPO{sub 4} is purely substitutional.

  13. Fluorescent lifetime measurements of rare-earth elements in gallium arsenide. Master's thesis

    SciTech Connect

    Topp, D.J.

    1990-12-01

    Lifetime measurements of the excited states of three GaAs semiconductors doped with the rare earth elements Erbium (Er), Praseodymium (Pr), and Thulium (Tm) has been studied using a pulsed nitrogen laser and germanium detector. The measurements were made with an experimental set up with a system response time of 0.34 microseconds. A 330 milliwatt nitrogen laser with a wavelength of 3370 angstroms was used to excite transitions of the rare earth elements.

  14. Experimental Parameters Affecting Stripping of Rare Earth Elements from Loaded Sorptive Media in Simulated Geothermal Brines

    DOE Data Explorer

    Dean Stull

    2016-05-24

    Experimental results from several studies exploring the impact of pH and acid volume on the stripping of rare earth elements (REEs) loaded onto ligand-based media via an active column. The REEs in this experiment were loaded onto the media through exposure to a simulated geothermal brine with known mineral concentrations. The data include the experiment results, rare earth element concentrations, and the experimental parameters varied.

  15. Developing alternative resources of rare earth elements in Europe - EURARE and the red mud challenge

    NASA Astrophysics Data System (ADS)

    Deady, Eimear; Mouchos, Evangelos; Goodenough, Kathryn; Wall, Frances; Williamson, Ben

    2015-04-01

    Novel Untapped European Resource?" ERES 1st European Rare Earth Resources conference, Milos, Greece, (5-6/09/2014). [7] A. Wagh and W. Pinnock, "Occurrence of scandium and rare earth elements in Jamaican bauxite waste", Economic Geology, vol. 82, no. 3, pp. 757-761, May 1987. [8] G. Mongelli, "Ce-anomalies in the textural components of Upper Cretaceous karst bauxites from the Apulian carbonate platform (southern Italy)", Chemical Geology, vol. 140, no. 1, pp. 69-79, June 1997. Additional resources: www.eurare.eu; www.redmud.org.

  16. Nioboaeschynite-(Ce), Ce(NbTi)O6

    PubMed Central

    Morrison, Shaunna M.; Downs, Robert T.; Domanik, Kenneth J.; Yang, Hexiong; Doell, Donald

    2012-01-01

    Nioboaeschynite-(Ce), ideally Ce(NbTi)O6 [cerium(III) niobium(V) titanium(IV) hexa­oxide; refined formula of the natural sample is Ca0.25Ce0.79(Nb1.14Ti0.86)O6], belongs to the aeschynite mineral group which is characterized by the general formula AB 2(O,OH)6, where eight-coordinated A is a rare earth element, Ca, Th or Fe, and six-coordinated B is Ti, Nb, Ta or W. The general structural feature of nioboaeschynite-(Ce) resembles that of the other members of the aeschynite group. It is characterized by edge-sharing dimers of [(Nb,Ti)O6] octa­hedra which share corners to form a three-dimensional framework, with the A sites located in channels parallel to the b axis. The average A—O and B—O bond lengths in nioboaeschynite-(Ce) are 2.471 and 1.993 Å, respectively. Moreover, another eight-coordinated site, designated as the C site, is also located in the channels and is partially occupied by A-type cations. Additionally, the refinement revealed a splitting of the A site, with Ca displaced slightly from Ce (0.266 Å apart), presumably resulting from the crystal-chemical differences between the Ce3+ and Ca2+ cations. PMID:22904701

  17. Seasonal dissolved rare earth element dynamics of the Amazon River main stem, its tributaries, and the Curuaí floodplain

    NASA Astrophysics Data System (ADS)

    Barroux, GwéNaëL.; Sonke, Jeroen E.; Boaventura, Geraldo; Viers, JéRôMe; Godderis, Yves; Bonnet, Marie-Paule; Sondag, Francis; Gardoll, SéBastien; Lagane, Christelle; Seyler, Patrick

    2006-12-01

    We present a comprehensive dissolved rare earth element (REE) data set for the Amazon River and its main tributaries, Rio Negro, Solimões, and Madeira, as well as the Curuaí floodplain. The two-year time series show that REE vary seasonally with discharge in each of the tributaries, and indicate a hydrologically dominated control. Upper crust normalized REE patterns are relatively constant throughout the year, with Ce/Ce* anomalies being positively related to discharge. We propose revised annual dissolved REE fluxes to the surface Atlantic Ocean based on an integration of the seasonal data. For Nd (<0.22 μm) this results in an average flux of 607 ± 43 T/yr, which is at least 1.6 times larger than the previous estimate of 374 T/yr (<0.45 μm) based on low water stage data. Moreover, during the high water season the maximum Nd flux measures 1277 t.yr-1, constituting 30% of the required flux to the Atlantic Ocean (Tachikawa et al., 2003). Consequently, a smaller contribution of Nd from atmospheric and river particle desorption is required than was previously suggested. A mass balance of Amazon tributaries and observed fluxes at Óbidos indicates that dissolved LREE behave quasi-conservatively. Conversely, the HREE mass balance presents a deficit during the high water stages, which could be related to the passage of water through the floodplain system accompanied by solid/dissolved phase transfer.

  18. Determination of Barium and selected rare-earth elements in geological materials employing a HpGe detector by radioisotope excited x-ray fluorescence

    SciTech Connect

    LaBrecque, J.J.; Preiss, I.L.

    1984-01-01

    The laterite material (geological) from Cerro Impacto was first studied by air radiometric techniques in the 1970's and was found to have an abnormally high radioactive background. Further studies showed this deposit to be rich in thorium, columbium, barium and rare-earth elements (mostly La, Ce, Pr and Nd). A similar work has been reported for the analysis of Brazil's lateritic material from Morro do Ferro to determine elemental compositions (including barium and rare-earth elements) and its relationship to the mobilization of thorium from the deposit using a Co-57 radioisotope source. The objective of this work was to develop an analytical method to determine barium and rare-earth element present in Venezuelan lateritic material from Cerro Impacto. We have employed a method before, employing a Si(Li) detector, but due to the low detection efficiencies in the rare-earth K-lines region (about 30 KeV - 40 KeV), we have decided to study the improvement in sensitivities and detection limits using an hyperpure germanium detector.

  19. Rare earth element recycling from waste nickel-metal hydride batteries.

    PubMed

    Yang, Xiuli; Zhang, Junwei; Fang, Xihui

    2014-08-30

    With an increase in number of waste nickel-metal hydride batteries, and because of the importance of rare earth elements, the recycling of rare earth elements is becoming increasingly important. In this paper, we investigate the effects of temperature, hydrochloric acid concentration, and leaching time to optimize leaching conditions and determine leach kinetics. The results indicate that an increase in temperature, hydrochloric acid concentration, and leaching time enhance the leaching rate of rare earth elements. A maximum rare earth elements recovery of 95.16% was achieved at optimal leaching conditions of 70°C, solid/liquid ratio of 1:10, 20% hydrochloric acid concentration, -74μm particle size, and 100min leaching time. The experimental data were best fitted by a chemical reaction-controlled model. The activation energy was 43.98kJ/mol and the reaction order for hydrochloric acid concentration was 0.64. The kinetic equation for the leaching process was found to be: 1-(1-x)(1/3)=A/ρr0[HCl](0.64)exp-439,8008.314Tt. After leaching and filtration, by adding saturated oxalic solution to the filtrate, rare earth element oxalates were obtained. After removing impurities by adding ammonia, filtering, washing with dilute hydrochloric acid, and calcining at 810°C, a final product of 99% pure rare earth oxides was obtained. PMID:25089667

  20. Precious metals and rare earth elements in municipal solid waste--sources and fate in a Swiss incineration plant.

    PubMed

    Morf, Leo S; Gloor, Rolf; Haag, Olaf; Haupt, Melanie; Skutan, Stefan; Di Lorenzo, Fabian; Böni, Daniel

    2013-03-01

    In Switzerland many kinds of waste, e.g. paper, metals, electrical and electronic equipment are separately collected and recycled to a large extent. The residual amount of municipal solid waste (MSW) has to be thermally treated before final disposal. Efforts to recover valuable metals from incineration residues have recently increased. However, the resource potential of critical elements in the waste input (sources) and their partitioning into recyclable fractions and residues (fate) is unknown. Therefore, a substance flow analysis (SFA) for 31 elements including precious metals (Au, Ag), platinum metal group elements (Pt, Rh) and rare earth elements (La, Ce, etc.) has been conducted in a solid waste incinerator (SWI) with a state-of-the-art bottom ash treatment according to the Thermo-Re® concept. The SFA allowed the determination of the element partitioning in the SWI, as well as the elemental composition of the MSW by indirect analysis. The results show that the waste-input contains substantial quantities of precious metals, such as 0.4 ± 0.2mg/kg Au and 5.3 ± 0.7 mg/kg Ag. Many of the valuable substances, such as Au and Ag are enriched in specific outputs (e.g. non-ferrous metal fractions) and are therefore recoverable. As the precious metal content in MSW is expected to rise due to its increasing application in complex consumer products, the results of this study are essential for the improvement of resource recovery in the Thermo-Re® process. PMID:23085306

  1. Experimental productivity rate optimization of rare earth element separation through preparative solid phase extraction chromatography.

    PubMed

    Knutson, Hans-Kristian; Max-Hansen, Mark; Jönsson, Christian; Borg, Niklas; Nilsson, Bernt

    2014-06-27

    Separating individual rare earth elements from a complex mixture with several elements is difficult and this is emphasized for the middle elements: Samarium, Europium and Gadolinium. In this study we have accomplished an overloaded one-step separation of these rare earth elements through preparative ion-exchange high-performance liquid chromatography with an bis (2-ethylhexyl) phosphoric acid impregnated column and nitric acid as eluent. An inductively coupled plasma mass spectrometry unit was used for post column element detection. The main focus was to optimize the productivity rate, subject to a yield requirement of 80% and a purity requirement of 99% for each element, by varying the flow rate and batch load size. The optimal productivity rate in this study was 1.32kgSamarium/(hmcolumn(3)), 0.38kgEuropium/(hmcolumn(3)) and 0.81kgGadolinium/(hmcolumn(3)). PMID:24835593

  2. Vanadium oxide bronzes containing rare-earth elements

    SciTech Connect

    Volkov, V.L.; Zubkov, V.G.; Fedyukov, A.S.; Zainulin, Yu.G.

    1988-05-01

    We attempted to make phases having the general formula Ln/sub x/V/sub 2/O/sub 5/ (Ln = La, Eu, Yb) without success; the specimens usually consisted of three phases: the rare-earth orthovanadate LnVO/sub 4/, vanadium(V) oxide, and VO/sub 2/. To shift the process to give Ln/sub x/V/sub 2/O/sub 5/, heat treatment was applied to mixtures of the initial high-purity substances. The x-ray patterns were recorded with a DRON-UM1 apparatus with Cr K..cap alpha.. radiation and were processed by the Poroshok program. The IR spectra were recorded with UR-20 spectrometer with oil mulls.

  3. Rare earth element and uranium-thorium variations in tufa deposits from the Mono Basin, CA

    NASA Astrophysics Data System (ADS)

    Wilcox, E. S.; Tomascak, P. B.; Hemming, N.; Hemming, S. R.; Rasbury, T.; Stine, S.; Zimmerman, S. R.

    2009-12-01

    Samples of fossil tufa deposits from several localities in the Mono Basin, eastern California, were analyzed for trace element concentrations in order to better understand changes in lake composition in the past. These deposits were formed during the last glacial cycle, mostly during deglaciation (Benson et al., 1990, PPP). Three elevations are represented by the analyses. Samples from near Highway 167 were sampled between 2063 and 2069 m asl. Samples from near Thompson Road were sampled between 2015 and 2021 m. One layered mound was sampled at 1955 m. Concentrations of the lanthanide rare earth elements (REE), in particular the heavy/light (HREE/LREE) distributions, have been shown to be sensitive to alkalinity in modern saline lakes (e.g., Johannesson et al., 1994, GRL, 21, 773-776), and the same has been suggested for U/Th (Anderson et al., 1982, Science, 216, 514-516). Holocene to near-modern tufa towers exist in shallow water and around the current shoreline (1945 m). Tufa towers above 2000 m include a characteristic morphology termed thinolite, interpreted to represent pseudomorphs after the very cold water mineral ikaite. Most lower elevation towers do not have the thinolite morphology, but some layered tufa mounds at low elevations include several layers of thinolite, such as the one sampled for this project. Analyses were made on millimeter-scale bulk samples from tufa towers. Measurements were made on sample solutions with a Varian 820MS quadrupole ICP-MS. Mono Basin tufa samples have total REE concentrations ranging from 0.029 to 0.77 times average shales. Samples have flat to moderately HREE-enriched shale-normalized patterns with limited overall variability ([La/Lu]SN of 1.8 to 9.6) but with some variability in the slope of the HREE portion of the patterns. Tufa towers sampled from three elevations have (Gd/Lu)SN of 0.40 to 1.5. The REE patterns of most samples have small positive Ce anomalies, but a minority of samples, all from the layered tufa mound

  4. [Effects of Arbuscular Mycorrhizal Fungi on the Growth and Ce Uptake of Maize Grown in Ce-contaminated Soils].

    PubMed

    Wang, Fang; Guo, Weil; Ma, Peng-kun; Pan, Liang; Zhang, Jun

    2016-01-15

    A greenhouse pot experiment was conducted to investigate the effects of arbuscular mycorrhizal (AM) fungi Glomus aggregatum (GA) and Funneliformis mosseae (FM) on AM colonization rate, biomass, nutrient uptake, C: N: P stoichiometric and Ce uptake and transport by maize (Zea mays L.) grown in soils with different levels of Ce-contaminated (100, 500 and 1000 mg x kg(-1)). The aim was to provide basic data and technical support for the treatment of soils contaminated by rare earth elements. The results indicated that symbiotic associations were successfully established between the two isolates and maize, and the average AM colonization rate ranged from 7. 12% to 74.47%. The increasing concentration of Ce in soils significantly decreased the mycorrhizal colonization rate, biomass, nutrition contents and transport rate of Ce from root to shoot of maize, and significantly increased C: P and N: P ratios and Ce contents in shoot and root of maize. Both AM fungi inoculations promoted the growth of maize, but the promoting role of FM was more significant than that of GA in severe Ce-contaminated soils. There were no significant differences in the growth of maize between two AM fungi in mild and moderate Ce-contaminated soils. Inoculation with AM fungi significantly improved nutritional status of maize by increasing nutrient uptake and decreasing C: N: P ratios. GA was more efficient than FM in enhancing nutrient uptake in mild and moderate Ce-contaminated soils, while FM was more efficient in severe Ce-contaminated soils. Moreover, inoculation with AM fungi significantly increased Ce contents of shoot and root in mild Ce-contaminated soils, but had no significant effect on Ce contents of maize in moderate and severe Ce-contaminated soils, and promoted the transport of Ce from root to shoot. The experiment demonstrates that AM fungi can alleviate toxic effects of Ce on plants and have a potential role in the phytoremediation of soils contaminated by rare earth elements. PMID

  5. Anomalous abundance and redistribution patterns of rare earth elements in soils of a mining area in Inner Mongolia, China.

    PubMed

    Wang, Lingqing; Liang, Tao

    2016-06-01

    The Bayan Obo Mine, the largest rare earth element (REE) deposit ever found in the world, has been mined for nearly 60 years for iron and rare earth elements. To assess the influences of mining activities on geochemical behavior of REEs in soils, 27 surface soil samples and three soil profile samples were collected from different directions in the vicinity of the mine area. The total concentrations of REEs in surface soils varied from 149.75 to 18,891.81 mg kg(-1) with an average value of 1906.12 mg kg(-1), which was apparently higher than the average values in China (181 mg kg(-1)). The order of the average concentrations of individual REEs in surface soils was similar to that in Bayan Obo ores, which confirmed that the concentration and distribution of REEs in the soils was influenced by the mining activities. The concentrations of single REE in the soil profiles showed a similar trend with depth with an increase at 0-25 cm section, then decreased and remained relatively stable in the deep part. The normalized curves inclined to the right side, showing the conspicuous fractionation between the light and heavy REEs, which supported by the North American Shale Composite (NASC) and Post-Archean Australian Shale (PAAS) normalized concentration ratios calculated for selected elements (La N /Yb N , La N /Sm N , Gd N /Yb N ). Slight positive Ce anomaly and negative Eu anomaly were also observed. PMID:26931660

  6. Determination of rare earth and concomitant elements in magnesium alloys by inductively coupled plasma optical emission spectrometry.

    PubMed

    Fariñas, Juan C; Rucandio, Isabel; Pomares-Alfonso, Mario S; Villanueva-Tagle, Margarita E; Larrea, María T

    2016-07-01

    An Inductively Coupled Plasma Optical Emission Spectrometry method for simultaneous determination of Al, Ca, Cu, Fe, In, Mn, Ni, Si, Sr, Y, Zn, Zr and rare earth elements (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) in magnesium alloys, including the new rare earth elements-alloyed magnesium, has been developed. Robust conditions have been established as nebulizer argon flow rate of 0.5mLmin(-1) and RF incident power of 1500W, in which matrix effects were significantly reduced around 10%. Three acid digestion procedures were performed at 110°C in closed PFA vessels heated in an oven, in closed TFM vessels heated in a microwave furnace, and in open polypropylene tubes with reflux caps heated in a graphite block. The three digestion procedures are suitable to put into solution the magnesium alloys samples. From the most sensitive lines, one analytical line with lack or low spectral interferences has been selected for each element. Mg, Rh and Sc have been studied as internal standards. Among them, Rh was selected as the best one by using Rh I 343.488nm and Rh II 249.078nm lines as a function of the analytical lines. The trueness and precision have been established by using the Certified Reference Material BCS 316, as well as by means of recovery studies. Quantification limits were between 0.1 and 9mgkg(-1) for Lu and Pr, respectively, in a 2gL(-1) magnesium matrix solution. The method developed has been applied to the commercial alloys AM60, AZ80, ZK30, AJ62, WE54 and AE44. PMID:27154648

  7. The surface sediment types and their rare earth element characteristics from the continental shelf of the northern south China sea

    NASA Astrophysics Data System (ADS)

    Wang, Shuhong; Zhang, Nan; Chen, Han; Li, Liang; Yan, Wen

    2014-10-01

    The grain size as well as some major and trace elements, including rare earth element (REE), for 273 surface sediment samples collected from the continental shelf of the northern South China Sea were analyzed in this study. The sediment types are mainly sandy silt and silt, making up 60% of the whole samples, and secondly are mud, sandy mud, muddy sand and silty sand, making up 28% of the whole samples, based on grain-size in which the Folk's classification was used. The total REE content (ΣREE) show a wide variation from 21 ppm to 244 ppm with an average value of 155 ppm, which similar to the average ΣREE of the China loess, but much different from that in deep-sea clay, showing a significant terrigenous succession. The REE contents in different sediment types vary greatly, mainly enriching in silt, sandy silt, mud and sandy mud. The REE distribution contours parallel to the coastal, presenting like strips and their contents gradually reduce with increasing distance from the coast. The high content of the western Pearl River Mouth, Shang/Xiachuan Islands and Hailing Bay might be regarded to the coastal current developed from the east to the west along to the Pearl River Mouth in the northern South China Sea. But the chondrite-normalized REE patterns in various sediment types have no difference, basically same as those of coastal rivers and upper crust. They all show relative enrichments in light rare earth element (LREE), noticeable negative Eu anomaly and no Ce anomaly, indicating that those sediments are terrigenous sediments and from the same source region. Further analysis suggest that the sedimentary environment in the study area is relatively stable and granite widely distributed in the South China mainland is the main source of REE, which are transported mainly by the Pearl River. The late diagenesis has little effect on the REE.

  8. Research of the entry of rare earth elements Eu3+ and La3+ into plant cell.

    PubMed

    Gao, Yongsheng; Zeng, Fuli; Yi, An; Ping, Shi; Jing, Lanhua

    2003-03-01

    Whether rare earth elements can enter into plant cells remains controversial. This article discusses the ultracellular structural localization of lanthanum (La(3+)) and europium (Eu(3+)) in the intact plant cells fed by rare earth elements Eu(3+) and La(3+). Eu-TTA fluorescence analysis of the plasmalemma, cytoplast, and mitochondria showed that Eu(3+) fluorescence intensities in such structures significantly increased. Eu(3+) can directly enter or be carried by the artificial ion carrier A23187 into plant cells through the calcium ion (Ca(2+)) channel and then partially resume the synthesis of amaranthin in the Amaranthus caudatus growing in the dark. Locations of rare earth elements La(3+) and Eu(3+) in all kinds of components of cytoplasmatic organelles were determined with transmission electron microscope, scanning electron microscope, and energy-dispersive X-ray microanalysis. The results of energy-dispersive X-ray microanalysis indicated that Eu(3+) and La(3+) can be absorbed into plant cells and bind to the membranes of protoplasm, chloroplast, mitochondrion, cytoplast, and karyon. These results provide experimental evidence that rare earth elements can be absorbed into plant cells, which would be the basis for interpreting physiological and biochemical effects of rare earth elements on plant cells. PMID:12663949

  9. Molecular Polyarsenides of the Rare-Earth Elements.

    PubMed

    Arleth, Nicholas; Gamer, Michael T; Köppe, Ralf; Konchenko, Sergey N; Fleischmann, Martin; Scheer, Manfred; Roesky, Peter W

    2016-01-22

    Reduction of [Cp*Fe(η(5)-As5)] with [Cp''2Sm(thf)] (Cp''=η(5)-1,3-(tBu)2C5H3) under various conditions led to [(Cp''2Sm)(μ,η(4):η(4)-As4)(Cp*Fe)] and [(Cp''2Sm)2As7(Cp*Fe)]. Both compounds are the first polyarsenides of the rare-earth metals. [(Cp''2Sm)(μ,η(4):η(4)-As4)(Cp*Fe)] is also the first d/f-triple decker sandwich complex with a purely inorganic planar middle deck. The central As4(2-) unit is isolobal with the 6π-aromatic cyclobutadiene dianion (CH)4(2-). [(Cp''2Sm)2As7(Cp*Fe)] contains an As7(3-) cage, which has a norbornadiene-like structure with two short As-As bonds in the scaffold. DFT calculations confirm all the structural observations. The As-As bond order inside the cyclo As4 ligand in [(Cp''2Sm)(μ,η(4):η(4)-As4)(Cp*Fe)] was estimated to be in between an As-As single bond and a formally aromatic As4(2-) system. PMID:26676537

  10. Evaluation of carbonate diagenesis: A comparative study of minor elements, trace elements, and rare-earth elements (REE + Y) between Pleistocene corals and matrices from Grand Cayman, British West Indies

    NASA Astrophysics Data System (ADS)

    Li, Rong; Jones, Brian

    2014-12-01

    On Grand Cayman, the Pleistocene Ironshore Formation consists of six unconformity-bounded units of limestones that have been partially or completely altered to calcite by post-depositional meteoric diagenesis. In order to examine the diagenetic history from the perspective of geochemical elements, the concentrations of minor element (Sr, Na, Mg), trace elements (Ba, Fe, Mn, Al, Si), and rare-earth elements (REE) and yttrium (Y) were determined for 105 corals and 84 matrices collected from the Rogers Wreck Point (RWP), Western Onshore area (WO), and offshore George Town (GT) areas. With the transformation of aragonite to calcite, the Sr, Na, and Ba values decreased, but Mg increased, which are indicative of diagenetic alteration in an open water system. Due to intrinsic "vital effects" and the extrinsic diagenetic environment, the variations of Sr, Na, Ba, and Mg concentrations between Acropora and Montastrea from the GT area are different to those of their counterparts from RWP and WO. The signatures of Sr, Na, Ba, and Mg are in good agreement with the diagenetic history as determined from petrographic and stable isotopic criteria. The REE + Y (REY) concentrations (ΣREY) are higher in the matrices (0.2-6.9 ppm, average 2.6 ppm) than in the associated corals (0.1-5.4 ppm, average 0.6 ppm). Shale-normalized REY patterns of the Pleistocene Ironshore Formation are similar to those of oxygenated seawater, which are characterized by (1) light REE depletion relative to heavy REE (average DySN/SmSN = 1.7, n = 35), (2) positive La anomalies (average Pr/Pr* = 1.17, n = 53), and (3) negative Ce anomalies (average Ce/Ce* = 0.49, n = 53). The preserved seawater-like REY distribution pattern, the lack of correlation between ΣREY and mineralogy, and the lack of correlation between ΣREY and diagenesis-sensitive stable oxygen isotope (δ18O) indicate that meteoric diagenesis did not have a major impact on the REY distribution patterns. The matrices and corals in the GT area

  11. Geochemical behaviors of rare earth elements in groundwater along a flow path in the North China Plain

    NASA Astrophysics Data System (ADS)

    Liu, Haiyan; Guo, Huaming; Xing, Lina; Zhan, Yanhong; Li, Fulan; Shao, Jingli; Niu, Hong; Liang, Xing; Li, Changqing

    2016-03-01

    Rare earth element (REE) geochemistry is a useful tool in delineating hydrogeochemical processes and tracing solute transport, which can be used to reveal groundwater chemical evolution in the complexed groundwater systems of the North China Plain (NCP). Groundwaters and sediments were collected approximately along a flow path in shallow and deep aquifers of the NCP to investigate REE geochemistry as a function of distance from the recharge zone. Groundwater REE concentrations are relatively low, with ranges from 81.2 to 163.6 ng/L in shallow groundwaters, and from 65.2 to 133.7 ng/L in deep groundwaters. Speciation calculation suggests that dissolved REEs mainly occur as dicarbonato (Ln(CO3)2-) and carbonato (LnCO3+) complexes. Although along the flow path groundwater REE concentrations do not vary substantially, relatively lower HREEs are observed in central plain (Zone II) compared to recharge area (Zone I) and discharge plain (Zone III). Shale-normalized REE patterns are characterized by different degrees of enrichment in the HREEs, as indicated by the variation in average (Er/Nd)NASC value. The similar REE compositions and shale-normalized REE patterns of shallow and deep groundwaters demonstrate that interactions of groundwaters between shallow and deep aquifers possibly occur, which is likely due to the long-term groundwater over-exploration. Cerium anomalies (Ce/Ce∗ = CeNASC/(LaNASC × PrNASC)0.5) generally increase from Zone I, through Zone II, to Zone III, with trends from 0.79 to 3.58, and from 1.22 to 2.43 in shallow groundwaters and deep groundwaters, respectively. This is consistent with the variations in oxidation-reduction potential and redox sensitive components (i.e., dissolved Fe, Mn, NO3- and As concentrations) along the flow path. Positive Ce anomaly and redox indicators suggest that redox conditions progressively evolve from oxic to moderate anaerobic in the direction of groundwater flow. In the recharge zone (Zone I), groundwater low

  12. Temporal trends (1981-2007) of trace and rare earth elements in the lichen Cetraria islandica (L.) Ach. from Italian herbaria.

    PubMed

    Minganti, Vincenzo; Drava, Giuliana; De Pellegrini, Rodolfo; Modenesi, Paolo; Malaspina, Paola; Giordani, Paolo

    2014-03-01

    Twenty-four herbarium specimens of Cetraria islandica collected in Italy from 1981 to 2007 were used for retrospective analysis. Cd, Ce, Cu, Fe, Gd, La, Mn, Ni, Pb, Sb, V, Y, and Zn concentrations were measured. Pb showed a negative temporal trend, linked to the ban of leaded fuel for vehicles. Pb showed a negative correlation with the distance of the sampling sites from a highway in the years before 1995 and no relationship after that year, corresponding to the Pb content reduction in gasoline. A significant trend towards increasing Mn concentrations over time also emerged, which deserves further investigations due to Mn toxicity. Cluster analysis showed a group of elements of anthropogenic origin, while rare earth elements formed a separated cluster of natural origin. Lichens from herbaria proved to be a valuable tool for reconstructing historical trends in trace element deposition, highlighting variations produced by human activities. PMID:24268754

  13. [Removal Characteristics of Elemental Mercury by Mn-Ce/molecular Sieve].

    PubMed

    Tan, Zeng-qiang; Niu, Guo-ping; Chen, Xiao-wen; An, Zhen

    2015-06-01

    The impregnation method was used to support molecular sieve with active manganese and cerium components to obtain a composite molecular sieve catalyst. The mercury removal performance of the catalyst was studied with a bench-scale setup. XPS analysis was used to characterize the sample before and after the modification in order to study the changes in the active components of the catalyst prepared. The results showed that the catalyst carrying manganese and cerium components had higher oxidation ability of elemental mercury in the temperature range of 300 degrees C - 450 degrees C, especially at 450 degrees C, the oxidation efficiency of elemental mercury was kept above 80%. The catalyst had more functional groups that were conducive to the oxidation of elemental mercury, and the mercury removal mainly depended on the chemical adsorption. The SO2 and NO in flue gas could inhibit the oxidation of elemental mercury to certain extent. PMID:26387298

  14. U.S. trade dispute with China over rare earth elements

    NASA Astrophysics Data System (ADS)

    Showstack, Randy

    2012-03-01

    The U.S. government has brought a new trade case against China over rare earth elements (REE) as well as tungsten and molybdenum, President Barack Obama announced on 13 March. Japan and the European Union also have taken similar actions against China about REEs, which are a group of 17 chemically similar metallic elements that are used in a variety of electronic, optical, magnetic, and catalytic applications. REEs are plentiful in the Earth's crust, although China currently has about 37% of the world's reserves and accounts for more than 95% of the world's production of the elements, according to the British Geological Survey. The United States has requested consultations with China at the World Trade Organization (WTO) concerning "China's unfair export restraints on rare earths, as well as tungsten and molybdenum," the Office of the United States Trade Representative announced in a 13 March statement.

  15. Alkali element depletion by core formation and vaporization on the early Earth

    NASA Technical Reports Server (NTRS)

    Lodders, K.; Fegley, B., Jr.

    1994-01-01

    The depletion of Na, K, Rb, and Cs in the Earth's upper mantle and crust relative to their abundances in chondrites is a long standing problem in geochemistry. Here we consider two commonly invoked mechanisms, namely core formation, and vaporization, for producing the observed depletions. Our models predict that a significant percentage of the Earth's bulk alkali element inventory is in the core (30 percent for Na, 52 percent for K, 74 percent for Rb, and 92 percent for Cs). These predictions agree with independent estimates from nebular volatility trends and (for K) from terrestrial heat flow data. Our models also predict that vaporization and thermal escape during planetary accretion are unlikely to produce the observed alkali element depletion pattern. However, loss during the putative giant impact which formed the Moon cannot be ruled out. Experimental, observational, and theoretical tests of our predictions are also described. Alkali element partitioning into the Earth's core was modeled by assuming that alkali element partitioning during core formation on the aubrite parent body (APB) is analogous to that on the early Earth. The analogy is reasonable for three reasons. First, the enstatite meteorites are the only known meteorites with the same oxygen isotope systematics as the Earth-Moon system. Second, the large core size of the Earth and the V depletion in the mantle requires accretion from planetesimals as reduced as the enstatite chondrites. Third, experimental studies of K partitioning between silicate and metal plus sulfide show that more K goes into the metal plus sulfide at higher pressures than at one atmosphere pressure. Thus partitioning in the relatively low pressure natural laboratory of the APB is a good guide to alkali elemental partitioning during the growth of the Earth.

  16. Addressing Rare-Earth Element Criticality: An Example from the Aviation Industry

    NASA Astrophysics Data System (ADS)

    Ku, Anthony Y.; Dosch, Christopher; Grossman, Theodore R.; Herzog, Joseph L.; Maricocchi, Antonio F.; Polli, Drew; Lipkin, Don M.

    2014-09-01

    Rare-earth (RE) elements are enablers for a wide range of technologies, including high-strength permanent magnets, energy-efficient lighting, high-temperature thermal barrier coatings, and catalysts. While direct material substitution is difficult in many of these applications because of the specific electronic, optical, or electrochemical properties imparted by the individual rare-earth elements, we describe an example from the aviation industry where supply chain optimization may be an option. Ceramic matrix composite engine components require environmental barrier coatings (EBCs) to protect them from extreme temperatures and adverse reactions with water vapor in the hot gas path. EBC systems based on rare-earth silicates offer a unique combination of environmental resistance, thermal expansion matching, thermal conductivity, and thermal stability across the service temperature window. Several pure rare-earth silicates and solid solutions have been demonstrated in EBC applications. However, all rely on heavy rare-earth elements (HREEs) for phase stability. This article considers the possibility of using separation tailings containing a mixture of HREEs as a source material in lieu of using the high-purity HREE oxides. This option arises because the desired properties of RE-silicate EBCs derive from the average cation size rather than the electronic properties of the individual rare-earth cations. Because separation tailings have not incurred the costs associated with the final stages of separation, they offer an economical alternative to high-purity oxides for this emerging application.

  17. Addressing Rare-Earth Element Criticality: An Example from the Aviation Industry

    NASA Astrophysics Data System (ADS)

    Ku, Anthony Y.; Dosch, Christopher; Grossman, Theodore R.; Herzog, Joseph L.; Maricocchi, Antonio F.; Polli, Drew; Lipkin, Don M.

    2014-11-01

    Rare-earth (RE) elements are enablers for a wide range of technologies, including high-strength permanent magnets, energy-efficient lighting, high-temperature thermal barrier coatings, and catalysts. While direct material substitution is difficult in many of these applications because of the specific electronic, optical, or electrochemical properties imparted by the individual rare-earth elements, we describe an example from the aviation industry where supply chain optimization may be an option. Ceramic matrix composite engine components require environmental barrier coatings (EBCs) to protect them from extreme temperatures and adverse reactions with water vapor in the hot gas path. EBC systems based on rare-earth silicates offer a unique combination of environmental resistance, thermal expansion matching, thermal conductivity, and thermal stability across the service temperature window. Several pure rare-earth silicates and solid solutions have been demonstrated in EBC applications. However, all rely on heavy rare-earth elements (HREEs) for phase stability. This article considers the possibility of using separation tailings containing a mixture of HREEs as a source material in lieu of using the high-purity HREE oxides. This option arises because the desired properties of RE-silicate EBCs derive from the average cation size rather than the electronic properties of the individual rare-earth cations. Because separation tailings have not incurred the costs associated with the final stages of separation, they offer an economical alternative to high-purity oxides for this emerging application.

  18. Anthropogenic gadolinium anomalies and rare earth elements in the water of Atibaia River and Anhumas Creek, Southeast Brazil.

    PubMed

    de Campos, Francisco Ferreira; Enzweiler, Jacinta

    2016-05-01

    The concentrations of rare earth elements (REE), measured in water samples from Atibaia River and its tributary Anhumas Creek, Brazil, present excess of dissolved gadolinium. Such anthropogenic anomalies of Gd in water, already described in other parts of the world, result from the use of stable and soluble Gd chelates as contrast agents in magnetic resonance imaging. Atibaia River constitutes the main water supply of Campinas Metropolitan area, and its basin receives wastewater effluents. The REE concentrations in water samples were determined in 0.22-μm pore size filtered samples, without and after preconcentration by solid-phase extraction with bis-(2-ethyl-hexyl)-phosphate. This preconcentration method was unable to retain the anthropogenic Gd quantitatively. The probable reason is that the Gd chelates dissociate slowly in acidic media to produce the free ion that is retained by the phosphate ester. Strong correlations between Gd and constituents or parameters associated with effluents confirmed the source of most Gd in water samples as anthropogenic. The shale-normalized REE patterns of Atibaia River and Anhumas Creek water samples showed light and heavy REE enrichment trends, respectively. Also, positive Ce anomalies in many Atibaia River samples, as well as the strong correlations of the REE (except Gd) with terrigenous elements, imply that inorganic colloidal particles contributed to the REE measured values. PMID:27068533

  19. Controls on the distribution and fractionation of yttrium and rare earth elements in core sediments from the Mandovi estuary, western India

    NASA Astrophysics Data System (ADS)

    Prajith, A.; Rao, V. Purnachandra; Kessarkar, Pratima M.

    2015-01-01

    Mineralogy, major elements (Fe, Mn and Al), rare earths and yttrium (REY) of bulk sediments were analyzed in four gravity cores recovered along the main channel of the Mandovi estuary, western India, to determine the sources and controls on REY distribution. The accelerator mass spectrometer (AMS) ages of total organic carbon indicated modern age for the sediments of the upper estuary and, maximum mean ages of 1588 years AD and 539 years AD for the bottom sediments of the cores in the lower estuary and bay, respectively. The sediments of the upper/middle estuary showed abundant hematite, magnetite and goethite and high Fe, Mn, total-REE (ΣREE) and Y, while those in the lower estuary/bay showed abundant silicate minerals and relatively low Fe, Mn, ΣREE and Y. ΣREE showed significant correlation with clay and silt fractions and Y, Al and organic carbon (OC) content of the sediments. The light to heavy REE ratios (LREE/HREE) of sediments were lower than in Post-Archean Australian Shale (PAAS). The PAAS-normalized rare earths and yttrium (REY; Y inserted between Dy and Ho) patterns of sediments showed middle REE (MREE)- and HREE-enrichment with positive Eu anomaly (Eu/Eu*) and variable Ce anomaly (Ce/Ce*). The REY of sediments is primarily controlled by its texture and REE of source sediment, which is ore material-dominated in the upper/middle estuary and silicate material-dominated in the lower estuary/bay. Low LREE/HREE ratios suggest that very fine-grained sediments were carried away from the estuary because of high-energy conditions. Fractionations of REY (Y/Ho, Sm/Nd, Ce/Ce* and Eu/Eu*) are controlled by different mechanisms. High Y/Ho ratios in clayey silts are due to redistribution of Y and Ho by adsorption onto organic-rich, clays. Variations in Sm/Nd ratios are similar to that of Eu/Eu* in cores from the lower estuary/bay and are controlled by mineral constituents of the sediments. Positive Ce and Eu anomalies are inherited from ore material, and ore

  20. Rare earth elements in coastal sediments of the northern Galician shelf: Influence of geological features

    NASA Astrophysics Data System (ADS)

    Prego, Ricardo; Caetano, Miguel; Bernárdez, Patricia; Brito, Pedro; Ospina-Alvarez, Natalia; Vale, Carlos

    2012-03-01

    The Northern coast of Galicia, NW Iberian Peninsula, exhibits a variety of geological features: Ortegal allochthonous complex, Ollo-de-Sapo autochthonous domain and massifs of Bares, Barqueiro and San-Ciprian. In order to examine the influence of terrestrial lithologies on coastal sediments, 103 samples were collected in the Rias of Ortigueira, Barqueiro and Viveiro, their neighbouring shelf and the estuaries of Mera, Sor and Landro rivers. Aluminium, Fe, Sc, particulate inorganic and organic carbon and rare earth elements (REE) were determined in the <2 mm fraction. In addition, calcite, muscovite, quartz and riebeckite minerals were identified and quantified in 33 selected samples. The distributions of riebeckite and Fe reflect the influence of Ortegal complex on the coastal areas around the Cape Ortegal. The highest concentrations of ΣREE were found in fine sediments from confined inner parts of the Rias (up to 233 mg kg-1), while most of the sands contained 11-70 mg kg-1. ΣREE normalised to European Shale (ES) highlights the relative abundance of lanthanides (ΣREEN>6) near Cape Ortegal and the innermost ria zones. The ratio between light and heavy REE (L/H) showed lower values (4-11) around Cape Ortegal and the shelf while higher ratios (15-23) were detected in west of the Cape Estaca-de-Bares and in the inner Viveiro Ria due to elevated contributions of La and Ce. The L/H values normalised to ES reflects the importance of HREE in the adjacent area to Ortegal Complex (LN/HN<0.8) and the LREE (LN/HN>1.4) in the inner estuaries and west Cape Estaca-de-Bares. The highest REE individual ES normalised were measured in fine-grained sediments of the Mera and Sor estuaries. Sediments from the eastern shelf of Cape Ortegal presented enhanced ratios only for HREE. These results indicate that distribution of REE in the northern Galician region is highly depending on the neighbouring lithological pattern, contrasting with the situation found in the western Galician

  1. [Ce3⁺/Tb3⁺ Doped Alkaline-Earth Borate Glasses Employed in Enhanced Solar Cells].

    PubMed

    Yang, Peng; Zhao, Xin; Wang, Zhi-qiang; Lin, Hai

    2015-12-01

    Ce³⁺ and Tb³⁺ doped alkaline earth borate (LKZBSB) glasses and the photoluminescence properties of glass system have been fabricated and investigated, and the observed violet and green fluorescences are originated from Ce³⁺ and Tb³⁺ emit- ting centers, respectively. Four emission bands peaked at 487, 543, 586 and 621 nm are attributed to the emission transitions ⁵D₄-->⁷F₆, ⁵D₄-->⁷F₅, ⁵D₄-->⁷F₄ and ⁵D₄-->⁷F₃ of Tb³⁺, respectively, and consists of a broad emission band peaking at 389 nm attributed to 5d--4ƒ electric dipole allowed transition of Ce³⁺. With the introduction of Ce³⁺, the effective excitation wavelength range of Tb³⁺ in LKZBSB glasses are remarkably expanded, and the enhanced factor of green fluorescence of Tb³⁺ in Ce³⁺/Tb³⁺ co-doped LKZBSB glasses is up to 73 times in medium-wavelength ultraviolet (UVB) excitation region, compared with that in Tb³⁺ single-doped case. The results show that the conversion from ultraviolet (UV) radiation to visible light is efficient in Ce³⁺/ Tb³⁺ doped LKZBSB glasses, demonstrating that the glasses have potential values in developing enhanced solar cell as a conver- sion layer. PMID:26964196

  2. Siderophore-promoted transfer of rare earth elements and iron from volcanic ash into glacial meltwater, river and ocean water

    NASA Astrophysics Data System (ADS)

    Bau, Michael; Tepe, Nathalie; Mohwinkel, Dennis

    2013-02-01

    The rare earth elements (REE) are a group of trace elements that have short marine residence times and that in river, lake and marine surface waters are typically associated with organic and inorganic particles. Explosive volcanic eruptions, such as the 2010 eruptions of Eyjafjallajökull volcano in Iceland, produce volcanic ash particles which can be an important source of iron and other nutrients for aquatic organisms. To become bioavailable, however, this iron needs to be solubilized by complexing agents, such as siderophores. A well-studied example of such a chelator is the biogenic siderophore desferrioxamin-B (DFOB). Based on results from incubation experiments with glacial meltwater-rich river waters from southern Iceland, which are rich in suspended volcanic ash and that had been incubated with and without DFOB, respectively, we here show that siderophores not only enhance the release of iron, but also promote the mobilization of REE from these particles. In the presence of DFOB, partial dissolution of volcanic ash (and presumably other lithic particles) produces a flux of dissolved REE into ambient waters, that is characterized by depletion of the light REE over the middle REE and by selective enrichment of cerium, due to the formation of dissolved Ce(IV)-DFOB complexes. In siderophore-rich environments, this siderophore-bound REE flux has the potential to modify the concentrations and distribution of the dissolved REE and of the isotopic composition of dissolved Nd in glacial meltwaters, river waters and seawater and might be a component of the boundary effects between shelf sediments and seawater, which are assumed to account for the “missing Nd flux” to seawater. Thermodynamic data further suggest that siderophore-promoted element mobilization could also be important for other polyvalent (trace) elements, such as Hf.

  3. Determination of trace rare earth elements in gadolinium aluminate by inductively coupled plasma time of flight mass spectrometry

    NASA Astrophysics Data System (ADS)

    Saha, Abhijit; Deb, S. B.; Nagar, B. K.; Saxena, M. K.

    An analytical methodology was developed for the precise quantification of ten trace rare earth elements (REEs), namely, La, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, and Tm, in gadolinium aluminate (GdAlO3) employing an ultrasonic nebulizer (USN)-desolvating device based inductively coupled plasma mass spectrometry (ICP-MS). A microwave digestion procedure was optimized for digesting 100 mg of the refractory oxide using a mixture of sulphuric acid (H2SO4), phosphoric acid (H3PO4) and water (H2O) with 1400 W power, 10 min ramp and 60 min hold time. An USN-desolvating sample introduction system was employed to enhance analyte sensitivities by minimizing their oxide ion formation in the plasma. Studies on the effect of various matrix concentrations on the analyte intensities revealed that precise quantification of the analytes was possible with matrix level of 250 mg L- 1. The possibility of using indium as an internal standard was explored and applied to correct for matrix effect and variation in analyte sensitivity under plasma operating conditions. Individual oxide ion formation yields were determined in matrix matched solution and employed for correcting polyatomic interferences of light REE (LREE) oxide ions on the intensities of middle and heavy rare earth elements (MREEs and HREEs). Recoveries of ≥ 90% were achieved for the analytes employing standard addition technique. Three real samples were analyzed for traces of REEs by the proposed method and cross validated for Eu and Nd by isotope dilution mass spectrometry (IDMS). The results show no significant difference in the values at 95% confidence level. The expanded uncertainty (coverage factor 1σ) in the determination of trace REEs in the samples were found to be between 3 and 8%. The instrument detection limits (IDLs) and the method detection limits (MDLs) for the ten REEs lie in the ranges 1-5 ng L- 1 and 7-64 μg kg- 1 respectively.

  4. Mineral chemistry of Rare Earth Element (REE) mineralization, Browns Ranges, Western Australia

    NASA Astrophysics Data System (ADS)

    Cook, Nigel J.; Ciobanu, Cristiana L.; O'Rielly, Daniel; Wilson, Robin; Das, Kevin; Wade, Benjamin

    2013-07-01

    ‘Green energy futures’ are driving unprecedented demand for Rare Earth Elements (REE), underpinning significant exploration activity worldwide. Understanding how economic REE concentrations form is critical for development of exploration models. REE mineralisation in the Browns Ranges, Gordon Downs Region, Western Australia, comprises xenotime-dominant mineralisation hosted within Archaean to Palaeoproterozoic metasedimentary units (Browns Range Metamorphics). Mineralogical, petrographic and mineral-chemical investigation, including trace element analysis by Laser-Ablation Inductively-Coupled Plasma Mass Spectroscopy, gives insights into the mineralogical distribution and partitioning of REE, and also provides evidence for the genetic evolution of the Browns Range REE mineralisation via a succession of hydrothermal processes. Two main REE-bearing minerals are identified: xenotime [(Y,REE)PO4], which is HREE selective; and subordinate florencite [(REEAl3(PO4)2(OH)6] which is LREE selective. Two morphological generations of xenotime are recognised; compositions are however consistent. Xenotime contains Dy (up to 6.5 wt.%), Er (up to 4.35 wt.%), Gd (up to 7.56 wt.%), Yb (up to 4.65 wt.%) and Y (up to 43.3 wt.%). Laser Ablation ICP-MS element mapping revealed a subtle compositional zoning in some xenotime grains. LREE appear concentrated in the grain cores or closest to the initial point of growth whereas HREE, particularly Tm, Yb and Lu, are highest at the outer margins of the grains. The HREE enrichment at the outer margins is mimicked by As, Sc, V, Sr, U, Th and radiogenic Pb. Florencite is commonly zoned and contains Ce (up to 11.54 wt.%), Nd (up to 10.05 wt.%) and La (up to 5.40 wt.%) and is also notably enriched in Sr (up to 11.63 wt.%) and Ca. Zircon (which is not a significant contributor of REEs overall due to its low abundance in the rocks) is also enriched in REE (up to 13 wt.% ΣREE) and is the principal host of Sc (up to 0.8 wt.%). Early, coarse

  5. Statistical Constraints from Siderophile Elements on Earth's Accretion, Differentiation, and Initial Core Stratification

    NASA Astrophysics Data System (ADS)

    O'Rourke, J. G.; Stevenson, D. J.

    2015-12-01

    Abundances of siderophile elements in the primitive mantle constrain the conditions of Earth's core/mantle differentiation. Core growth occurred as Earth accreted from collisions between planetesimals and larger embryos of unknown original provenance, so geochemistry is directly related to the overall dynamics of Solar System formation. Recent studies claim that only certain conditions of equilibration (pressure, temperature, and oxygen fugacity) during core formation can reproduce the available data. Typical analyses, however, only consider the effects of varying a few out of tens of free parameters in continuous core formation models. Here we describe the Markov chain Monte Carlo method, which simultaneously incorporates the large uncertainties on Earth's composition and the parameterizations that describe elemental partitioning between metal and silicate. This Bayesian technique is vastly more computationally efficient than a simple grid search and is well suited to models of planetary accretion that involve a plethora of variables. In contrast to previous work, we find that analyses of siderophile elements alone cannot yield a unique scenario for Earth's accretion. Our models predict a wide range of possible light element contents for the core, encompassing all combinations permitted by seismology and mineral physics. Specifically, we are agnostic between silicon and oxygen as the dominant light element, and the addition of carbon or sulfur is also permissible but not well constrained. Redox conditions may have remained roughly constant during Earth's accretion or relatively oxygen-rich material could have been incorporated before reduced embryos. Pressures and temperatures of equilibration, likewise, may only increase slowly throughout accretion. Therefore, we do not necessarily expect a thick (>500 km), compositionally stratified layer that is stable against convection to develop at the top of the core of Earth (or, by analogy, Venus). A thinner stable layer

  6. Rare earth element and stable isotope (O, S) geochemistry of barite from the Bijgan deposit, Markazi Province, Iran

    NASA Astrophysics Data System (ADS)

    Ehya, Farhad

    2012-01-01

    The Bijgan barite deposit, which is located northeast of Delijan in Markazi Province of Iran, occurs as a small lenticular body at the uppermost part of an Eocene volcano-sedimentary rock unit. The presence of fossiliferous and carbonaceous strata suggests that the host rocks were deposited in a quiet marine sedimentary environment. Barite, calcite, iron oxides and carbonaceous clay materials are found as massive patches as well as thin layers in the deposit. Barite is marked by very low concentrations of Sr (1-2%) and total amounts of rare earth elements (REEs) (6.25-17.39 ppm). Chondrite-normalized REE patterns of barite indicate a fractionation of light REEs (LREEs) from La to Sm, similar to those for barite of different origins from elsewhere. The LaCN/LuCN ratios and chondrite-normalized REE patterns reveal that barite in the Bijgan deposit is enriched in LREE relative to heavy rare earth elements (HREEs). The similarity between the Ce/La ratios in the barite samples and those found in deep-sea barite supports a marine origin for barite. Lanthanum and Gd exhibit positive anomalies, which are common features of marine chemical sediments. Cerium shows a negative anomaly in most samples that was inherited from the negative Ce anomaly of hydrothermal fluid that mixed with seawater at the time of barite precipitation. The δ18O values of barites show a narrow range of 9.1-11.4‰, which is close to or slightly lower than that of contemporaneous seawater at the end of the Eocene. This suggests a contribution of oxygen from seawater in the barite-forming solution. The δ34S values of barites (9.5-15.3‰) are lower than that of contemporaneous seawater, which suggests a contribution of magmatic sulfur to the ore-forming solution. The oxygen and sulfur isotope ratios indicate that submarine hydrothermal vent fluids are a good analog for solutions that precipitated barite, due to similarities in the isotopic composition of the sulfates. The available data including

  7. Rare earth element content of thermal fluids from Surprise Valley, California

    DOE Data Explorer

    Andrew Fowler

    2015-09-23

    Rare earth element measurements for thermal fluids from Surprise Valley, California. Samples were collected in acid washed HDPE bottles and acidified with concentrated trace element clean (Fisher Scientific) nitric acid. Samples were pre-concentratated by a factor of approximately 10 using chelating resin with and IDA functional group and measured on magnetic sector ICP-MS. Samples include Seyferth Hot Springs, Surprise Valley Resort Mineral Well, Leonard's Hot Spring, and Lake City Mud Volcano Boiling Spring.

  8. Potassium chloride and rare earth elements improve plant growth and increase the frequency of the Agrobacterium tumefaciens-mediated plant transformation.

    PubMed

    Boyko, Alex; Matsuoka, Aki; Kovalchuk, Igor

    2011-04-01

    Plant transformation efficiency depends on the ability of the transgene to successfully interact with plant host factors. Our previous work and the work of others showed that manipulation of the activity of host factors allows for increased frequency of transformation. Recently we reported that exposure of tobacco plants to increased concentrations of ammonium nitrate increases the frequency of both homologous recombination and plant transgenesis. Here we tested the influence of KCl and salts of rare earth elements, Ce and La on the efficiency of Agrobacterium-mediated plant transformation. We found that exposure to KCl, CeCl(3) and LaCl(3) leads to an increase in recombination frequency in Arabidopsis and tobacco. Plants grown in the presence of CeCl(3) and LaCl(3) had higher biomass, longer roots and greater root number. Analysis of transformation efficiency showed that exposure of tobacco plants to 50 mM KCl resulted in ~6.0-fold increase in the number of regenerated calli and transgenic plants as compared to control plants. Exposure to various concentrations of CeCl(3) showed a maximum increase of ~3.0-fold in both the number of calli and transgenic plants. Segregation analysis showed that exposure to KCl and cerium (III) chloride leads to more frequent integrations of the transgene at a single locus. Analysis of transgene intactness showed better preservation of right T-DNA border during transgene integration. Our data suggest that KCl and CeCl(3) can be effectively used to improve quantity and quality of transgene integrations. PMID:21132499

  9. Radioluminescence and thermoluminescence of rare earth element and phosphorus-doped zircon

    SciTech Connect

    Karali, T.; Can, N.; Townsend, P.D.; Rowlands, A.P.; Hanchar, J.M.

    2000-06-01

    The radioluminescence and thermoluminescence spectra of synthetic zircon crystals doped with individual trivalent rare earth element (REE) ions (Pr, Sm, Eu, Gd, Dy, Ho, Er, and Yb) and P are reported in the temperature range 25 to 673 K. Although there is some intrinsic UV/blue emission from the host lattice, the dominant signals are from the rare-earth sites, with signals characteristic of the REE{sup 3+} states. The shapes of the glow curves are different for each dopant, and there are distinct differences between glow peak temperatures for different rare-earth lines of the same element. Within the overall set of signals there are indications of linear trends in which some glow peak temperatures vary as a function of the ionic size of the rare earth ions. The temperature shifts of the peaks are considerable, up to 200{degree}, and much larger than those cited in other rare-earth-doped crystals of LaF{sub 3} and Bi{sub 4}Ge{sub 3}O{sub 12}. The data clearly suggest that the rare-earth ions are active both in the trapping and luminescence steps, and hence the TL occurs within localized defect complexes that include REE{sup 3+} ions.

  10. Composition of the earth's upper mantle. I - Siderophile trace elements in ultramafic nodules

    NASA Technical Reports Server (NTRS)

    Morgan, J. W.; Wandless, G. A.; Petrie, R. K.; Irving, A. J.

    1981-01-01

    The considered investigation is concerned with a reexamination of the question of the distribution of siderophile elements in the earth's upper mantle, taking into account a more unified data base which is now available. A comprehensive suite of ultramafic inclusions was collected as part of the Basaltic Volcanism Study Project and has been analyzed by instrument neutron activation analysis for major, minor, and some lithophile trace elements. In addition, 18 of these rocks and the important sheared garnet lherzolite PHN 1611 have been analyzed by means of radiochemical neutron activation analysis for 7 siderophile elements (Au, Ge, Ir, Ni, Os, Pd, and Re) and 9 volatile elements (Ag, Bi, Cd, In, Sb, Se, Te, Tl, and Zn). The siderophile element data reveal interesting inter-element correlations, which were not apparent from the compiled abundance tables of Ringwood and Kesson (1976) and Chou (1978).

  11. Preliminary study on using rare earth elements to trace non-point source phosphorous loss

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The environmental fate of phosphorus (P) is of concern as P is a primary cause of freshwater eutrophication. Rare earth elements (REEs) have been successfully used in the analysis of soil erosion and pollutant sources, as well as in the analysis of mineral genesis. To better understand the potential...

  12. Undecaprenyl Pyrophosphate Involvement in Susceptibility of Bacillus subtilis to Rare Earth Elements

    PubMed Central

    Ochi, Kozo

    2012-01-01

    The rare earth element scandium has weak antibacterial potency. We identified a mutation responsible for a scandium-resistant phenotype in Bacillus subtilis. This mutation was found within the uppS gene, which encodes undecaprenyl pyrophosphate synthase, and designated uppS86 (for the Thr-to-Ile amino acid substitution at residue 86 of undecaprenyl pyrophosphate synthase). The uppS86 mutation also gave rise to increased resistance to bacitracin, which prevents cell wall synthesis by inhibiting the dephosphorylation of undecaprenyl pyrophosphate, in addition to enhanced amylase production. Conversely, overexpression of the wild-type uppS gene resulted in increased susceptibilities to both scandium and bacitracin. Moreover, the mutant lacking undecaprenyl pyrophosphate phosphatase (BcrC) showed increased susceptibility to all rare earth elements tested. These results suggest that the accumulation of undecaprenyl pyrophosphate renders cells more susceptible to rare earth elements. The availability of undecaprenyl pyrophosphate may be an important determinant for susceptibility to rare earth elements, such as scandium. PMID:22904278

  13. Tracing sediment movement on semi-arid watershed using Rare Earth Elements 1988

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A multi-tracer method employing rare earth elements (REE) was used to determine sediment yield and to track sediment movement in a small semiarid watershed. A 0.33 ha watershed near Tombstone, AZ was divided into five morphological units, each tagged with one of five REE oxides. Relative contributi...

  14. A LOW-COST RARE EARTH ELEMENTS RECOVERY TECHNOLOGY - PHASE I

    EPA Science Inventory

    Physical Sciences, Inc., and the University of Kentucky Center for Applied Energy Research propose to develop a unique enabling technology to significantly reduce U.S. dependency for Rare Earth Elements (REE) on foreign suppliers and our global competitors. Our innovation...

  15. SEDIMENT REWORKING AND TRANSPORT IN EASTERN LAKE SUPERIOR: IN SITU RARE EARTH ELEMENT TRACER STUDIES

    EPA Science Inventory

    A rare earth element (REE) tracer pellet was deployed at the floor of the Ile Parisienne basin of eastern Lake Superior to measure representative sediment reworking and transport processes in the benthic boundary layer of the prnfundal Great Lakes. Samarium oxide, a high neutron-...

  16. Catalytic Graphitization of Coal-Based Carbon Materials with Light Rare Earth Elements.

    PubMed

    Wang, Rongyan; Lu, Guimin; Qiao, Wenming; Yu, Jianguo

    2016-08-30

    The catalytic graphitization mechanism of coal-based carbon materials with light rare earth elements was investigated using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, selected-area electron diffraction, and high-resolution transmission electron microscopy. The interface between light rare earth elements and carbon materials was carefully observed, and two routes of rare earth elements catalyzing the carbon materials were found: dissolution-precipitation and carbide formation-decomposition. These two simultaneous processes certainly accelerate the catalytic graphitization of carbon materials, and light rare earth elements exert significant influence on the microstructure and thermal conductivity of graphite. Moreover, by virtue of praseodymium (Pr), it was found that a highly crystallographic orientation of graphite was induced and formed, which was reasonably attributed to the similar arrangements of the planes perpendicular to (001) in both graphite and Pr crystals. The interface between Pr and carbon was found to be an important factor for the orientation of graphite structure. PMID:27482724

  17. Fluid rare earth element anlayses from wells RN-12 and RN-19, Reykjanes, Iceland

    DOE Data Explorer

    Andrew Fowler

    2015-07-24

    Results for fluid rare earth elment analyses from Reykjanes wells RN-12 and RN-19. The data have not been corrected for flashing. Samples preconcetrated using chelating resin with IDA functional group (InertSep ME-1). Analyzed using and Element magnetic sctor ICP-MS.

  18. Technical Information Resource on Rare Earth Elements Now Available to Public and Private Sector Stakeholders

    EPA Science Inventory

    A new EPA technical information resource, “Rare Earth Elements: A Review of Production, Processing, Recycling, and Associated Environmental Issues” has been produced as an introductory resource for those interested in learning more about REE mining and alternatives to meet demand...

  19. Studying the volatility of pyrazolone complexes of rare-earth elements by means of Knudsen effusion

    NASA Astrophysics Data System (ADS)

    Lazarev, N. M.; Petrov, B. I.; Bochkarev, L. N.; Safronova, A. V.; Abakumov, G. A.; Arapova, A. V.; Bessonova, Yu. A.

    2014-08-01

    The temperature dependences of the pressure of saturated vapor of pyrazolone complexes of rare-earth elements Ln(PMIP)3 (where Ln = Y, Ho, Er, Tm, Lu; PMIP = 1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone) are studied via Knudsen effusion, and the enthalpy of their sublimation is determined. Mass spectra and differential scanning calorimetry data are obtained.

  20. Compilation of Rare Earth Element Analyses from US Geothermal Fields and Mid Ocean Ridge Hydrothermal Vents

    DOE Data Explorer

    Andrew Fowler

    2015-10-01

    Compilation of rare earth element and associated major and minor dissolved constituent analytical data for USA geothermal fields and global seafloor hydrothermal vents. Data is in original units. Reference to and use of this data should be attributed to the original authors and publications according to the provisions outlined therein.

  1. Method to Recover Media Ligand Losses During Sorption of Rare Earth Elements from Simulated Geothermal Brines

    DOE Data Explorer

    Dean Stull

    2016-05-24

    This document describes the method and results of an in-situ experiment used to confirm that ligand bleed from a sorptive media can be contained. The experiment focused on maintaining the media's sorption of rare earth elements (REE) obtained from a simulated geothermal brine doped with known mineral concentrations.

  2. Geochemical characteristics of rare earth elements in soil of the Ditru Massif, Eastern Carpathians, Romania

    NASA Astrophysics Data System (ADS)

    Ion, Adriana

    2013-04-01

    The present paper describes the level of rare earth elements in soils developed from Ditrău massif area for evaluating of the background of these elements and accurate assessment of environmental impact. Also this paper contributed to understanding the important role of parent rocks in pedogenic processes. The Ditrău Alkaline Massif represent an intrusion body with a internal zonal structure, which was emplaced into pre-Alpine metamorphic rocks of the Bucovinian nappe complex close the Neogene - Quaternary volcanic arc of the Calimani-Guurghiu- Harghita Mountain chain. The center of massif was formed by nepheline syenite, which is surrounded by syenite and monazonite. North-western and north-eastern marginal sectors are composed of hornblende gabbro/hornblendite, alkali diorite, monzodiorite, monzosyenites and alkali granite. Small discrete ultramafic bodies (kaersutite-bearing peridotite, olivine, pyroxenite and hornblendite) and alkali gabbros occur in the Jolotca area. All this rocks are cut by late-stage dykes with a large variety of composition including tinguaite, phonolite, nepheline syenite, microsyenite, and aplite. The types of soils predominant in this zone are lithosoils. These soils are shallow developed, have low content in organic matter and reflects mineralogical and geochemical composition of the bedrock. The soil samples were collected from 70 location for all type of representative rocks (approximately 10 soil sampling points for each type of rock). The samples were analyzed by inductively coupled plasma mass spectrometry (ICP-MS). The pH values of these samples varied from 3.6 to 7.3, in general, the soils from massif area are acid or weakly acidic. The pH controls the abundance of REE in soil, the concentration of REE increases with decreasing pH values. In soil samples analyzed the contents of REE follow the order: Ce > La > Nd > Pr > Sm > Eu > Gd > Dy > Yb > Er > Tb > Ho >Tm. ∑ REE varied from 52.59 μg g-1 to 579.2 μg g-1 , the average

  3. Precious metals and rare earth elements in municipal solid waste – Sources and fate in a Swiss incineration plant

    SciTech Connect

    Morf, Leo S.; Gloor, Rolf; Haag, Olaf; Haupt, Melanie; Skutan, Stefan; Lorenzo, Fabian Di; Böni, Daniel

    2013-03-15

    Highlights: ► We carefully addressed all the very valuable comments and suggestions of the reviewers. ► We also have shortened the size of the paper and tried simplify it substantially, as requested by the reviewers (introduction 25% reduced!). ► We have decided to take the chance and have replaced the data for the “additional” elements (Cu, Cd, Zn, Pb, Sn, Cr, Ni, Fe, Al) of the earlier MFA (Morf, 2011) with data that belong to the samples of this study. ► We are convinced that with the revision the paper has significantly improved in quality and attractiveness. - Abstract: In Switzerland many kinds of waste, e.g. paper, metals, electrical and electronic equipment are separately collected and recycled to a large extent. The residual amount of municipal solid waste (MSW) has to be thermally treated before final disposal. Efforts to recover valuable metals from incineration residues have recently increased. However, the resource potential of critical elements in the waste input (sources) and their partitioning into recyclable fractions and residues (fate) is unknown. Therefore, a substance flow analysis (SFA) for 31 elements including precious metals (Au, Ag), platinum metal group elements (Pt, Rh) and rare earth elements (La, Ce, etc.) has been conducted in a solid waste incinerator (SWI) with a state-of-the-art bottom ash treatment according to the Thermo-Re® concept. The SFA allowed the determination of the element partitioning in the SWI, as well as the elemental composition of the MSW by indirect analysis. The results show that the waste-input contains substantial quantities of precious metals, such as 0.4 ± 0.2 mg/kg Au and 5.3 ± 0.7 mg/kg Ag. Many of the valuable substances, such as Au and Ag are enriched in specific outputs (e.g. non-ferrous metal fractions) and are therefore recoverable. As the precious metal content in MSW is expected to rise due to its increasing application in complex consumer products, the results of this study are

  4. Scanning Electron Microscope-Cathodoluminescence Analysis of Rare-Earth Elements in Magnets.

    PubMed

    Imashuku, Susumu; Wagatsuma, Kazuaki; Kawai, Jun

    2016-02-01

    Scanning electron microscope-cathodoluminescence (SEM-CL) analysis was performed for neodymium-iron-boron (NdFeB) and samarium-cobalt (Sm-Co) magnets to analyze the rare-earth elements present in the magnets. We examined the advantages of SEM-CL analysis over conventional analytical methods such as SEM-energy-dispersive X-ray (EDX) spectroscopy and SEM-wavelength-dispersive X-ray (WDX) spectroscopy for elemental analysis of rare-earth elements in NdFeB magnets. Luminescence spectra of chloride compounds of elements in the magnets were measured by the SEM-CL method. Chloride compounds were obtained by the dropwise addition of hydrochloric acid on the magnets followed by drying in vacuum. Neodymium, praseodymium, terbium, and dysprosium were separately detected in the NdFeB magnets, and samarium was detected in the Sm-Co magnet by the SEM-CL method. In contrast, it was difficult to distinguish terbium and dysprosium in the NdFeB magnet with a dysprosium concentration of 1.05 wt% by conventional SEM-EDX analysis. Terbium with a concentration of 0.02 wt% in an NdFeB magnet was detected by SEM-CL analysis, but not by conventional SEM-WDX analysis. SEM-CL analysis is advantageous over conventional SEM-EDX and SEM-WDX analyses for detecting trace rare-earth elements in NdFeB magnets, particularly dysprosium and terbium. PMID:26739864

  5. Serum Proteomic Analysis Based on iTRAQ in Miners Exposed to Soil Containing Rare Earth Elements.

    PubMed

    Liu, Heming; Wang, Jianzhong; Yang, Zenghua; Wang, Kunzheng

    2015-10-01

    To explore the toxic effects of rare earth elements (REEs) accumulated in human body, adopting the inductively coupled plasma mass spectrometry (ICP-MS) method, the present study measured REEs and the contents of eight other elements (Ca, Fe, Cu, Na, K, Zn, Mg, and P) in the hair of eight persons exposed to soil containing REEs for a long time as well as in the control group. In addition, proteomic analysis of serum of the two groups was conducted by isobaric tags for relative and absolute quantitation (iTRAQ) technique. Experimental results show that in the hair of the two groups, 15 REEs and eight other elements were detected, in which the content of La, Ce, Pr, Nd, Tb, Ho, Tm, Yb, and Fe in the exposure group is significantly higher than that of the control group, but the content of Ca in the exposure group is significantly lower than that of the control group; analysis yields out 29 differentially expressed proteins, in which 16 proteins are upregulated and 13 proteins are downregulated. Bioinformatics analysis of differentially expressed proteins demonstrates that they participate in various biological processes and five Kyoto Encyclopedia of Genes and Genomes (KEGG) pathways, forming an interaction network. Besides, some differentially expressed proteins may be related to neurovirulence, hepatotoxicity, pathological fibrosis, osteoporosis, and anticoagulation caused by REEs. The present experiment investigated the toxic effects of REEs accumulated in human body at the molecular level, which may lay a foundation for the future research of biological effect, threshold limit values, protection from exposure, and reasonable application of REEs. PMID:25800652

  6. Synthesis and crystal structure of the isotypic rare earth thioborates Ce[BS{sub 3}], Pr[BS{sub 3}], and Nd[BS{sub 3}

    SciTech Connect

    Hunger, Jens; Borna, Marija; Kniep, Ruediger

    2010-03-15

    The orthothioborates Ce[BS{sub 3}], Pr[BS{sub 3}] and Nd[BS{sub 3}] were prepared from mixtures of the rare earth (RE) metals together with amorphous boron and sulfur summing up to the compositions CeB{sub 3}S{sub 6}, PrB{sub 5}S{sub 9} and NdB{sub 3}S{sub 6}. The following preparation routes were used: solid state reactions with maximum temperatures of 1323 K and high-pressure high-temperature syntheses at 1173 K and 3 GPa. Pr[BS{sub 3}] and Nd[BS{sub 3}] were also obtained from rare earth chlorides RECl{sub 3} and sodium thioborate Na{sub 2}B{sub 2}S{sub 5} by metathesis type reactions at maximum temperatures of 1073 K. The crystal structure of the title compounds was determined from X-ray powder diffraction data. The thioborates are isotypic and crystallize in the orthorhombic spacegroup Pna2{sub 1} (No. 33; Z=4; Ce: a=7.60738(6)A, b=6.01720(4)A, c=8.93016(6)A; Pr: a=7.56223(4)A, b=6.00876(2)A, c=8.89747(4)A; Nd: a=7.49180(3)A, b=6.00823(2)A, c=8.86197(3)A) . The crystal structures contain isolated [BS{sub 3}]{sup 3-} groups with boron in trigonal-planar coordination. The sulfur atoms form the vertices of undulated kagome nets, which are stacked along [100] according to the sequence ABAB. Within these nets every second triangle is occupied by boron and the large hexagons are centered by rare earth ions, which are surrounded by overall nine sulfur species. - Abstract: Graphical Abstract Legend (TOC Figure): Table of Contents Figure The isotypic orthothioborates Ce[BS{sub 3}], Pr[BS{sub 3}] and Nd[BS{sub 3}] were prepared using different preparation routes. The crystal structure of the title compounds was determined from X-ray powder diffraction data. The crystal structures contain isolated [BS{sub 3}]{sup 3-} groups with boron in trigonal-planar coordination. The sulfur atoms form the vertices of corrugated kagome nets (sketched with blue dotted lines), which are stacked along [100] according to the sequence ABAB. Within these nets every second triangle is

  7. Simultaneous removal of elemental mercury and NO from flue gas by V2O5-CeO2/TiO2 catalysts

    NASA Astrophysics Data System (ADS)

    Zhang, Xunan; Li, Caiting; Zhao, Lingkui; Zhang, Jie; Zeng, Guangming; Xie, Yin'e.; Yu, Ming'e.

    2015-08-01

    A series of Ce-doped V2O5/TiO2 catalysts synthesized by an ultrasound assisted impregnation method were employed to investigate simultaneous removal of elemental mercury (Hg0) and NO in lab-scale experiments. Scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET), X-ray diffractogram (XRD), and X-ray photoelectron spectroscopy (XPS) analyses were used to characterize the samples. Compared to TiO2 support, the catalytic performance of CeO2 doped on both TiO2 and V2O5/TiO2 catalysts have been improved. Remarkably, 1%V2O5-10% CeO2/TiO2 (V1Ce10Ti) exhibited the highest Hg0 oxidation efficiency of 81.55% at 250 °C with a desired NO removal efficiency under the same condition. Both the NO conversion and Hg0 oxidation efficiency were enhanced in the presence of O2. The activity was inhibited by the injection of NH3 with the increase of NH3/NO. When in the presence of 400 ppm SO2, Hg0 oxidation was slightly affected. Furthermore, Hg0 removal behavior under both oxidation and selective catalytic reduction (SCR) condition over V1Ce10Ti were well investigated to further probe into the feasibility of one single unit for multi-pollutants control in industry application. The existence of the redox cycle of V4+ + Ce4+ ↔ V5+ + Ce3+ in V2O5-CeO2/TiO2 catalyst could not only greatly improve the NO conversion, but also promote the oxidation of Hg0.

  8. Thorium, uranium and rare earth elements content in lanthanide concentrate (LC) and water leach purification (WLP) residue of Lynas advanced materials plant (LAMP)

    NASA Astrophysics Data System (ADS)

    AL-Areqi, Wadeeah M.; Majid, Amran Ab.; Sarmani, Sukiman

    2014-02-01

    Lynas Advanced Materials Plant (LAMP) has been licensed to produce the rare earths elements since early 2013 in Malaysia. LAMP processes lanthanide concentrate (LC) to extract rare earth elements and subsequently produce large volumes of water leach purification (WLP) residue containing naturally occurring radioactive material (NORM). This residue has been rising up the environmental issue because it was suspected to accumulate thorium with significant activity concentration and has been classified as radioactive residue. The aim of this study is to determine Th-232, U-238 and rare earth elements in lanthanide concentrate (LC) and water leach purification (WLP) residue collected from LAMP and to evaluate the potential radiological impacts of the WLP residue on the environment. Instrumental Neutron Activation Analysis and γ-spectrometry were used for determination of Th, U and rare earth elements concentrations. The results of this study found that the concentration of Th in LC was 1289.7 ± 129 ppm (5274.9 ± 527.6Bq/kg) whereas the Th and U concentrations in WLP were determined to be 1952.9±17.6 ppm (7987.4 ± 71.9 Bq/kg) and 17.2 ± 2.4 ppm respectively. The concentrations of Th and U in LC and WLP samples determined by γ- spectrometry were 1156 ppm (4728 ± 22 Bq/kg) & 18.8 ppm and 1763.2 ppm (7211.4 Bq/kg) &29.97 ppm respectively. This study showed that thorium concentrations were higher in WLP compare to LC. This study also indicate that WLP residue has high radioactivity of 232Th compared to Malaysian soil natural background (63 - 110 Bq/kg) and come under preview of Act 304 and regulations. In LC, the Ce and Nd concentrations determined by INAA were 13.2 ± 0.6% and 4.7 ± 0.1% respectively whereas the concentrations of La, Ce, Nd and Sm in WLP were 0.36 ± 0.04%, 1.6%, 0.22% and 0.06% respectively. This result showed that some amount of rare earth had not been extracted and remained in the WLP and may be considered to be reextracted.

  9. Thorium, uranium and rare earth elements content in lanthanide concentrate (LC) and water leach purification (WLP) residue of Lynas advanced materials plant (LAMP)

    SciTech Connect

    AL-Areqi, Wadeeah M. Majid, Amran Ab. Sarmani, Sukiman

    2014-02-12

    Lynas Advanced Materials Plant (LAMP) has been licensed to produce the rare earths elements since early 2013 in Malaysia. LAMP processes lanthanide concentrate (LC) to extract rare earth elements and subsequently produce large volumes of water leach purification (WLP) residue containing naturally occurring radioactive material (NORM). This residue has been rising up the environmental issue because it was suspected to accumulate thorium with significant activity concentration and has been classified as radioactive residue. The aim of this study is to determine Th-232, U-238 and rare earth elements in lanthanide concentrate (LC) and water leach purification (WLP) residue collected from LAMP and to evaluate the potential radiological impacts of the WLP residue on the environment. Instrumental Neutron Activation Analysis and γ-spectrometry were used for determination of Th, U and rare earth elements concentrations. The results of this study found that the concentration of Th in LC was 1289.7 ± 129 ppm (5274.9 ± 527.6Bq/kg) whereas the Th and U concentrations in WLP were determined to be 1952.9±17.6 ppm (7987.4 ± 71.9 Bq/kg) and 17.2 ± 2.4 ppm respectively. The concentrations of Th and U in LC and WLP samples determined by γ- spectrometry were 1156 ppm (4728 ± 22 Bq/kg) and 18.8 ppm and 1763.2 ppm (7211.4 Bq/kg) and 29.97 ppm respectively. This study showed that thorium concentrations were higher in WLP compare to LC. This study also indicate that WLP residue has high radioactivity of {sup 232}Th compared to Malaysian soil natural background (63 - 110 Bq/kg) and come under preview of Act 304 and regulations. In LC, the Ce and Nd concentrations determined by INAA were 13.2 ± 0.6% and 4.7 ± 0.1% respectively whereas the concentrations of La, Ce, Nd and Sm in WLP were 0.36 ± 0.04%, 1.6%, 0.22% and 0.06% respectively. This result showed that some amount of rare earth had not been extracted and remained in the WLP and may be considered to be reextracted.

  10. Study on Orbital Decay of Near Earth Satellites with KS Orthogonal Elements

    NASA Astrophysics Data System (ADS)

    Ps, Sandeep

    STUDY ON ORBITAL DECAY OF NEAR EARTH SATELLITES WITH KS ORTHOGONAL ELEMENTS SANDEEP P S The knowledge of satellite orbit decay and its expected life prior to launch is necessary for mission planning purpose. Several sets of data for various parametric studies is sought quite often, it is necessary to minimize computational time involved for generating decay predictions, keeping the prediction accuracy normally good. A number of factors play dominant role in perturbation modelling for near earth satellites such as oblateness of the Earth, presence of the atmosphere, luni-solar attraction and solar radiation pressure. This paper concerns with the study of orbital decay of near earth satellites with KS orthogonal elements, which provide accurate orbit predictions at low computational time. Perturbations considered are due to oblateness of the Earth and the atmospheric drag. The Earth’s zonal harmonic terms J2 to J6 are included and the drag is modeled with an analytical diurnally oblate atmosphere. Effect of Earth’s geomagnetic and solar activity is included in density and density scale height computations. JACCHIA77 atmospheric model is utilized. The developed software is validated with the orbital data of decayed objects taken from www.space-track.org.

  11. Origin of the earth's moon - Constraints from alkali volatile trace elements

    NASA Technical Reports Server (NTRS)

    Kreutzberger, M. E.; Drake, M. J.; Jones, J. H.

    1986-01-01

    Although the moon is depleted in volatile elements compared to the earth, these depletions are not in accord with simple volatility. For example, the Cs/Rb ratios of the earth and moon inferred from basalt are approximately one seventh and one half of the CI ratio, respectively. Volatility considerations alone predict that the lunar Cs/Rb ratio should be equal to or lower than the terrestrial ratio if the moon was derived entirely from earth mantle material. Thus hypotheses such as rotational fission which invoke derivation of lunar material entirely from the earth's mantle may be excluded. The collisional ejection hypothesis of lunar origin requires at least 18 percent of lunar material to be derived from a projectile with dehydrated CI composition to match the lunar Cs/Rb ratio, and 25-50 percent to match both the lunar Cs/Rb ratio and absolute concentrations of Cs and Rb. It remains to be demonstrated that this relatively large contribution of projectile material is consistent with other elemental abundances and element ratios in the moon.

  12. Rare earth elements of seep carbonates: Indication for redox variations and microbiological processes at modern seep sites

    NASA Astrophysics Data System (ADS)

    Feng, Dong; Lin, Zhijia; Bian, Youyan; Chen, Duofu; Peckmann, Jörn; Bohrmann, Gerhard; Roberts, Harry H.

    2013-03-01

    At marine seeps, methane is microbially oxidized resulting in the precipitation of carbonates close to the seafloor. Methane oxidation leads to sulfate depletion in sediment pore water, which induces a change in redox conditions. Rare earth element (REE) patterns of authigenic carbonate phases collected from modern seeps of the Gulf of Mexico, the Black Sea, and the Congo Fan were analyzed. Different carbonate minerals including aragonite and calcite with different crystal habits have been selected for analysis. Total REE content (ΣREE) of seep carbonates varies widely, from 0.1 ppm to 42.5 ppm, but a common trend is that the ΣREE in microcrystalline phases is higher than that of the associated later phases including micospar, sparite and blocky cement, suggesting that ΣREE may be a function of diagenesis. The shale-normalized REE patterns of the seep carbonates often show different Ce anomalies even in samples from a specific site, suggesting that the formation conditions of seep carbonates are variable and complex. Overall, our results show that apart from anoxic, oxic conditions are at least temporarily common in seep environments.

  13. Rapid and precise determination of natural carbonate rare earth elements in femtogram quantities by ICP-SF-MS

    NASA Astrophysics Data System (ADS)

    Wu, C.; Liu, Y.; Shen, C.

    2011-12-01

    A rapid and precise technique for measuring of femtogram quantity rare earth elements (REE) levels in natural carbonate samples by ICP-SF-MS has been developed at the Department of Geosciences, National Taiwan University. REE/Ca ratios are calculated directly from the intensities of the ion beams of 46Ca, 139La, 140Ce, 141Pr, 146Nd, 147Sm, 153Eu, 160Gd, 159Tb, 163Dy, 165Ho, 166Er, 169Tm, 172Yb, and 175Lu using external matrix-matched synthetic standards to correct for instrumental ratio drifting and mass discrimination. A routine measurement time of 3 minutes is typical for one sample containing 20-40-ppm [Ca]. Replicate measurements made on natural coral and foraminiferal samples with REE/Ca ratios of 2-242 nmol/mol show external precisions of 1.9-6.5% (2RSD) can be achieved with only 10-1000 femtogram REEs in 10-20 μg carbonate consumed. The key advantages of this established technique are (1) to provide a possibility of directly analyzing REE isotopic composition in femtogram quantities without chemical separation steps, and (2) to potentially offer high precision and high temporal resolution REE records for diverse carbonates, such as corals, foraminifera, sclerosponges, tufa, and speleothems.

  14. Mineralogy and geochemistry of trace and Rare Earth Element from the Manaila massive sulphide deposit (Eastern Carpathians, Romania)

    NASA Astrophysics Data System (ADS)

    Moldoveanu, S.; Iancu, O. G.; Kasper, H. U.

    2012-04-01

    Keywords: Eastern Carpathians, Mănăila deposit, REE, trace elements, pyrite The present paper deal with the mineralogy and trace elements geochemistry of sulphide deposits from Mănăila mine field located in NE area of Eastern Carpathians Mountains (Romania). The mineralization occurs within metamorphic rocks of Tulgheş terrane, part of Crystalline-Mezozoic zone of the Eastern Carpathians. The metamorphic rocks in Mănăila area consist of felsic metavolcanics rocks with quartzites and quartz-feldspathic rocks as prevailing types. The P-T metamorphic conditions are typical of greenschis facies with biotite and garnet (Mn-Grt) in mineral assemblage. The mineralogical study was performed using reflected light microscope and Scanning Electron Microscopy (SEM) methods. Thus, the both methods show that the main sulphides minerals are represented by pyrite and chalcopyrite, being followed by sphalerite, galena and little amount of Cu sulphosalts (tetrahedrite and bournonite) and also by gangue minerals (quartz and carbonates). Pyrite occurs as large euhedral to subhedral grains in quartz and small rounded inclusion in chalcopyrite. The trace elements analysis was achieved on whole-rock samples and involved the determination of REE, LIL (Rb, Ba, Sr) and HFS (Y, Zr, Hf, U, Th, Nb, Ta) by ICP-MS method. The concentration of LIL and HFS trace elements in mineralized rocks decrease as follows: Ba > Bi > As > Sb > Co > Ga > Ni > Cd. Even if the barium contents in Mănăila ore is high, baritina (BaSO4) was not identified throught the mineralogical analyses carried out so far. The total rare earth element content (REE) of the samples from Mănăila range from 26.84 to 246.46 ppm. Chondrite - normalized REE patterns of the mineralized rocks show that the LREE are enriched in relation to the HREE. Also a positive Ce anomalies and negative Eu anomalies are present. Y/Ho and Zr/Hf ratios are close to the chondritic ratios indicating Charge-and-Radius-Controlled (CHARAC

  15. Heavy metals and rare earth elements source-sink in some Egyptian cigarettes as determined by neutron activation analysis.

    PubMed

    Nada, A; Abdel-Wahab, M; Sroor, A; Abdel-Haleem, A S; Abdel-Sabour, M F

    1999-07-01

    Heavy metals and rare earth elements in two types of cigarettes were studied. The contents of trace elements were determined by using delayed neutron activation analysis. In the present study 11 elements have been detected in popular and fine brand cigarettes marketed in Egypt. Evaluation of these elements with their potential hazards for smokers is briefly discussed. The material balance (source and sink) for each element was determined. Also the ratio of element recovery to the total amount was assessed. PMID:10376325

  16. Structural Responses and Finite Element Modeling of Hakka Tulou Rammed Earth Structures

    NASA Astrophysics Data System (ADS)

    Sranislawski, Daniel

    Hakka Tulous are rammed earth structures that have survived the effects of aging and natural elements upwards of even over a thousand years. These structures have housed the Hakka people of the Fujian Province, China in natural yet modern housing that has provided benefits over newer building materials. The key building material, rammed earth, which is used for the walls of the Hakka Tulou structures, has provided structural stability along with thermal comfort to the respective inhabitants of the Hakka Tulous. Through material testing and analysis this study has examined how the Tulou structures have maintained their structural stability while also providing thermal comfort. Reports of self healing cracks in the rammed earth walls were also analyzed for their validity in this study. The study has found that although the story of the self healing crack cannot be validated, there is reason to believe that with the existence of lime, some type of autogenous healing could occur on a small scale. The study has also found, through the use of nondestructive testing, that both the internal wooden systems (flooring, roof, and column support) and the rammed earth walls, are still structurally sound. Also, rammed earth's high thermal mass along with the use of sufficient shading has allowed for a delay release of heat energy from the walls of the Tulous, thus providing thermal comfort that can be felt during both night and day temperatures. The Hakka Tulou structures have been found to resist destruction from natural disasters such as strong earthquakes even when more modern construction has not. Through finite element modeling, this study has shown that the high volume of rammed earth used in the construction of the Hakka Tulous helps dissipate lateral force energy into much lower stresses for the rammed earth wall. This absorption of lateral force energy allows the rammed earth structures to survive even the strongest of earthquakes experienced in the region. The Hakka

  17. Rare Earth Element - Humic Acid Interaction: Experimental Evidence for Kinetic and Equilibrium Fractionation in Aqueous Systems.

    NASA Astrophysics Data System (ADS)

    Sonke, J. E.; Salters, V. J.; Benedetti, M. F.

    2003-12-01

    Dissolved organic matter (DOM) is well known for it's strong binding capacity for trace metals. In order to better predict the role of DOM in the speciation and transport of trace metals in the environment we coupled capillary electrophoresis (CE), a molecular separation technique, to a Sector Field Inductively Coupled Plasma Mass Spectrometer (SF-ICP-MS). The combination of these two techniques allows for the study of non-labile metal speciation in aquatic samples. By separating Rare Earth Element (REE) complexes with EDTA and Humic Acid's (i.e. ligand competition) we have been able to determine conditional equilibrium binding constants (Kc) and kinetic rate constants for all 14 REE's with Humic (HA) and Fulvic Acids (FA) as a function of pH (6-9) and ionic strength (IS, 0.01-0.1 mol/L). Assuming a 1:1 binding mechanism, logKc values for REE-FA varied from 9.0 (La) to 10.5 (Lu) at pH 6, 0.1 mol/L IS, and 11.7 (La) to 14.6 (Lu) at pH 9, 0.1 mol/L IS. LogKc values for REE-HA were 10.6 (La) to 12.2 (Lu) at pH 6, 0.1 mol/L IS and 13.2 (La) to 16.5 (Lu) at pH 9, 0.1 mol/L IS. Slightly higher values for Kc were obtained at 0.01 mol/L IS. The general observations of stronger REE-HA binding compared to REE-FA, and stronger binding with increasing pH and decreasing IS correlate with our current understanding of metal-DOM interactions (1). Both Kc's as well as kinetic rate constants increase with increasing REE mass number (decreasing ionic radius); a reflection of the well-known lanthanide contraction. This is the first comprehensive metal binding dataset between REE and DOM, and the first experimental evidence for differential equilibrium and kinetic binding behavior between REE's and DOM. The 30-1000 fold increase in binding strength of heavy REE's with DOM provides for a an equilibrium fractionation mechanism that may explain features of the global geochemical REE cycle such as fractionation related to weathering, estuarine mixing, and REE scavenging in the deep ocean

  18. Accurate projected augmented wave (PAW) datasets for rare-earth elements (RE=La-Lu)

    NASA Astrophysics Data System (ADS)

    Topsakal, Mehmet; Wentzcovitch, Renata

    2015-03-01

    We provide accurate projected augmented wave (PAW) datasets for rare-earth (RE) elements with some suggested Hubbard U values allowing efficient plane-wave calculations. Solid state tests of generated datasets were performed on rare-earth nitrides. Through density of state (DOS) and equation of state (EoS) comparisons, generated datasets were shown to yield excellent results comparable to highly accurate all-electron full-potential linearized augmented plane-wave plus local orbital (FLAPW+LO) calculations. Hubbard U values for trivalent RE ions are determined according to hybrid functional calculations. We believe that these new and open-source PAW datasets will allow further studies on rare-earth materials. NSF/EAR 1319361

  19. Highly siderophile elements were stripped from Earth's mantle by iron sulfide segregation.

    PubMed

    Rubie, David C; Laurenz, Vera; Jacobson, Seth A; Morbidelli, Alessandro; Palme, Herbert; Vogel, Antje K; Frost, Daniel J

    2016-09-01

    Highly siderophile elements (HSEs) are strongly depleted in the bulk silicate Earth (BSE) but are present in near-chondritic relative abundances. The conventional explanation is that the HSEs were stripped from the mantle by the segregation of metal during core formation but were added back in near-chondritic proportions by late accretion, after core formation had ceased. Here we show that metal-silicate equilibration and segregation during Earth's core formation actually increased HSE mantle concentrations because HSE partition coefficients are relatively low at the high pressures of core formation within Earth. The pervasive exsolution and segregation of iron sulfide liquid from silicate liquid (the "Hadean matte") stripped magma oceans of HSEs during cooling and crystallization, before late accretion, and resulted in slightly suprachondritic palladium/iridium and ruthenium/iridium ratios. PMID:27609889

  20. Rare-earth metal(III) oxide selenides M4O4Se[Se2] (M=La, Ce, Pr, Nd, Sm) with discrete diselenide units: crystal structures, magnetic frustration, and other properties.

    PubMed

    Strobel, Sabine; Choudhury, Amitava; Dorhout, Peter K; Lipp, Christian; Schleid, Thomas

    2008-06-01

    The rare-earth metal(III) oxide selenides of the formula La4O4Se[Se2], Ce4O4Se[Se2], Pr4O4Se[Se2], Nd4O4Se[Se2], and Sm4O4Se[Se2] were synthesized from a mixture of the elements with selenium dioxide as the oxygen source at 750 degrees C. Single crystal X-ray diffraction was used to determine their crystal structures. The isostructural compounds M4O4Se[Se2] (M=La, Ce, Pr, Nd, Sm) crystallize in the orthorhombic space group Amm2 with cell dimensions a=857.94(7), b=409.44(4), c=1316.49(8) pm for M=La; a=851.37(6), b=404.82(3), c=1296.83(9) pm for M=Ce; a=849.92(6), b=402.78(3), c=1292.57(9) pm for M=Pr; a=845.68(4), b=398.83(2), c=1282.45(7) pm for M=Nd; and a=840.08(5), b=394.04(3), c=1263.83(6) pm for M=Sm (Z=2). In their crystal structures, Se2- anions as well as [Se-Se]2- dumbbells interconnect {[M4O4]4+} infinity 2 layers. These layers are composed of three crystallographically different, distorted [OM4]10+ tetrahedra, which are linked via four common edges. The compounds exhibit strong Raman active modes at around 215 cm(-1), which can be assigned to the Se-Se stretching vibration. Optical band gaps for La4O4Se[Se2], Ce4O4Se[Se2], Pr4O4Se[Se2], Nd4O4Se[Se2], and Sm4O4Se[Se2] were derived from diffuse reflectance spectra. The energy values at which absorption takes place are typical for semiconducting materials. For the compounds M4O4Se[Se2] (M=La, Pr, Nd, Sm) the fundamental band gaps, caused by transitions from the valence band to the conduction band (VB-CB), lie around 1.9 eV, while for M=Ce an absorption edge occurs at around 1.7 eV, which can be assigned to f-d transitions of Ce3+. Magnetic susceptibility measurements of Ce4O4Se[Se2] and Nd4O4Se[Se2] show Curie-Weiss behavior above 150 K with derived experimental magnetic moments of 2.5 micro B/Ce and 3.7 micro B/Nd and Weiss constants of theta p=-64.9 K and theta p=-27.8 K for the cerium and neodymium compounds, respectively. Down to 1.8 K no long-range magnetic ordering could be detected. Thus, the large

  1. Thulium anomalies and rare earth element patterns in meteorites and Earth: Nebular fractionation and the nugget effect

    NASA Astrophysics Data System (ADS)

    Dauphas, Nicolas; Pourmand, Ali

    2015-08-01

    This study reports the bulk rare earth element (REEs, La-Lu) compositions of 41 chondrites, including 32 falls and 9 finds from carbonaceous (CI, CM, CO and CV), enstatite (EH and EL) and ordinary (H, L and LL) groups, as well as 2 enstatite achondrites (aubrite). The measurements were done in dynamic mode using multi-collector inductively coupled plasma mass spectrometers (MC-ICPMS), allowing precise quantification of mono-isotopic REEs (Pr, Tb, Ho and Tm). The CI-chondrite-normalized REE patterns (LaN/LuN; a proxy for fractionation of light vs. heavy REEs) and Eu anomalies in ordinary and enstatite chondrites show more scatter in more metamorphosed (petrologic types 4-6) than in unequilibrated (types 1-3) chondrites. This is due to parent-body redistribution of the REEs in various carrier phases during metamorphism. A model is presented that predicts the dispersion of elemental and isotopic ratios due to the nugget effect when the analyzed sample mass is limited and elements are concentrated in minor grains. The dispersion in REE patterns of equilibrated ordinary chondrites is reproduced well by this model, considering that REEs are concentrated in 200 μm-size phosphates, which have high LaN/LuN ratios and negative Eu anomalies. Terrestrial rocks and samples from ordinary and enstatite chondrites display negative Tm anomalies of ∼-4.5% relative to CI chondrites. In contrast, CM, CO and CV (except Allende) show no significant Tm anomalies. Allende CV chondrite shows large excess Tm (∼+10%). These anomalies are similar to those found in group II refractory inclusions in meteorites but of much smaller magnitude. The presence of Tm anomalies in meteorites and terrestrial rocks suggests that either (i) the material in the inner part of the solar system was formed from a gas reservoir that had been depleted in refractory dust and carried positive Tm anomalies or (ii) CI chondrites are enriched in refractory dust and are not representative of solar composition for

  2. Symmetric charge-transfer cross sections of IIIa rare-earth-metal elements

    SciTech Connect

    Hashida, Masaki; Sakabe, Shuji; Izawa, Yasukazu

    2011-03-15

    Symmetric charge-transfer cross sections of IIIa rare-earth-metal elements (Sc, Y, and Gd) in the impact energy range of 30 to 1000 eV were measured for the first time. The experiments were performed with a crossed-beam apparatus that featured primary ion production by photoionization with a tunable dye laser. Comparing the cross sections of IIIa rare-earth-metal elements ({sigma}{sub Sc}, {sigma}{sub Y}, and {sigma}{sub Gd}) with those of alkali metals or helium {sigma}{sub 0}, we found that {sigma}{sub 0{approx_equal}{sigma}Sc}<{sigma}{sub Y}<{sigma}{sub Gd{approx_equal}}2{sigma}{sub 0}at an impact energy of 1000 eV.

  3. Bishop tuff revisited: new rare Earth element data consistent with crystal fractionation.

    PubMed

    Cameron, K L

    1984-06-22

    The Bishop Tuff of eastern California is the type example of a high-silica rhyolite that, according to Hildreth, supposedly evolved by liquid-state differentiation. New analyses establish that the Bishop Tuff "earlyllate" rare earth element trend reported by Hildreth mimics the relations between groundmass glasses and whole rocks for allanite-bearing pumice. Differences in elemental concentrations between whole rock and groundmass are the result of phenocryst precipitation; thus the data of Hildreth are precisely those expected to result from crystal fractionation. PMID:17837193

  4. Preparation with a facile template-free method of uniform-sized mesoporous microspheres of rare earth (La, Ce, Pr, Nd) oxides

    SciTech Connect

    Ji, Pengfei; Xing, Mingyang; Bagwasi, Segomotso; Tian, Baozhu; Chen, Feng; Zhang, Jinlong

    2011-11-15

    Highlights: {yields} Mesoporous microspheres of light rare earth hydroxycarbonates and oxides were fabricated. {yields} The supersaturated urea has important effect on formation of mesoporous microspheres. {yields} The influences of [cation]/[urea] ratio and amount of water on the formation of spherical crystallites were discussed. -- Abstract: Mesoporous microspheres of light rare earth (La, Ce, Pr, Nd) hydroxycarbonates and oxides were successfully fabricated by a facile surfactant free hydrothermal method in supersaturated aqueous urea solution. The techniques of XRD, TEM, SEM, TG/DTA and N{sub 2} adsorption-desorption were employed to investigate the structure and formation process of mesoporous microspheres. It was revealed that supersaturated urea not only serve as a reactant and pH modifier in the reaction system but also guide the oriented assembly of hydroxycarbonate crystallites into microspheres by acting as a structure-directing agent. The microspheres of rare earth oxides could easily be obtained by simple calcination of corresponding hydroxycarbonates precursors without undergoing morphology changes. In addition, the influences of rare earth precursor and urea concentrations on the formation of microspheres were also investigated.

  5. The effect of particulate dissolution on the neodymium (Nd) isotope and Rare Earth Element (REE) composition of seawater

    NASA Astrophysics Data System (ADS)

    Pearce, Christopher R.; Jones, Morgan T.; Oelkers, Eric H.; Pradoux, Catherine; Jeandel, Catherine

    2013-05-01

    The exchange of material between particulates and seawater along the continental margins, a process commonly referred to as boundary exchange, is thought to play a significant role in controlling the neodymium (Nd) isotope and Rare Earth Element (REE) composition of the oceans. This study provides experimental verification of this concept by quantifying the effect of particulate dissolution in seawater on dissolved ɛNd and REE compositions. Three closed-system experiments were performed using basaltic particulate material of riverine, estuarine and marine origin. The release of Nd from this basaltic material increased the ɛNd composition of seawater in all three experiments, with a ɛNd value close to that of the associated sediment being achieved within 80 days in all experiments. Mass balance indicates that up to 0.4% of Nd from the particulate phase was released to the seawater over the duration of these experiments, and that the rate of release varied according to particulate origin and surface area. Progressive variations in the PAAS normalised REE patterns, as well as the Eu and Ce anomalies and La/Yb ratio, demonstrate that REEs were also transferred from the basaltic particulates to seawater during the experiments. Despite evidence for the release of REEs from the particulate material, dissolved REE abundances decreased during the experiments, and are thought to reflect incorporation into the REE-phosphate mineral rhabdophane. Together these experimental results confirm that elemental release from basaltic sediments on the ocean margins is a significant marine flux that can have a major control on the composition of seawater.

  6. Investigation of the separation of scandium and rare earth elements from red mud by use of reversed-phase HPLC.

    PubMed

    Tsakanika, Lambrini V; Ochsenkühn-Petropoulou, Maria Th; Mendrinos, Leonidas N

    2004-07-01

    A chromatographic method has been developed for separation and determination of scandium (Sc) and rare earth elements (REEs) in samples from a red mud (RM)-utilization process. Reversed-phase high-performance liquid chromatography (RP-HPLC) with post-column derivatization using 4-(2-pyridylazo)-resorcinol (PAR) and UV-visible detection at 520 nm was tested using different gradient elution profiles and pH values to optimize separation and recovery, primarily for Sc but also for yttrium and the individual lanthanides, from iron present in the samples. The separation was performed in less than 20 min by use of a mobile phase gradient. The concentration of alpha-hydroxyisobutyric acid ( alpha-HIBA), as eluent, was altered from 0.06 to 0.4 mol L(-1) (pH 3.7) and 0.01 mol L(-1) sodium salt n-octane sulfonic acid (OS) was used as modifier. Very low detection limits in the nanogram range and a good resolution for Sc and REEs except for Y/Dy were achieved. Before application of the method to the red mud samples and to the corresponding bauxites, Sc and REEs were leached from red mud with 0.6 mol L(-1) HNO(3) and mostly separated, as a group, from the main elements by ion exchange/selective elution (6 mol L(-1) HNO(3)) in accordance with a pilot-plant process developed in this laboratory. After evaporation of the eluent to dryness the extracted elements were re-dissolved in the mobile phase. By use of this chromatographic method Sc, which is the most expensive of the elements investigated and occurs in economically interesting concentrations in red mud, could be separated not only from co-existing Fe but also from Y/Dy, Yb, Er, Ho, Gd, Eu, Sm, Nd, Pr, Ce and La. All the elements investigated were individually recovered. Their recoveries were found to be nearly quantitative. PMID:15221192

  7. Study on the removal of elemental mercury from simulated flue gas by Fe₂O₃-CeO₂/AC at low temperature.

    PubMed

    Wang, Yan; Li, Caiting; Zhao, Lingkui; Xie, Yin'e; Zhang, Xunan; Zeng, Guangming; Wu, Huiyu; Zhang, Jie

    2016-03-01

    Fe2O3 and CeO2 modified activated coke (AC) synthesized by the equivalent-volume impregnation were employed to remove elemental mercury (Hg(0)) from simulated flue gas at a low temperature. Effects of the mass ratio of Fe2O3 and CeO2, reaction temperature, and individual flue gas components including O2, NO, SO2, and H2O (g) on Hg(0) removal efficiency of impregnated AC were investigated. The samples were characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Results showed that with optimal mass percentage of 3 % Fe2O3 and 3 % CeO2 on Fe3Ce3/AC, the Hg(0) removal efficiency could reach an average of 88.29 % at 110 °C. Besides, it was observed that O2 and NO exhibited a promotional effect on Hg(0) removal, H2O (g) exerted a suppressive effect, and SO2 showed an insignificant inhibition without O2 to some extent. The analysis of XPS indicated that the main species of mercury on used Fe3Ce3/AC was HgO, which implied that adsorption and catalytic oxidation were both included in Hg(0) removal. Furthermore, the lattice oxygen, chemisorbed oxygen, and/or weakly bonded oxygen species made a contribution to Hg(0) oxidation. PMID:26552788

  8. CeO2-TiO2 catalysts for catalytic oxidation of elemental mercury in low-rank coal combustion flue gas.

    PubMed

    Li, Hailong; Wu, Chang-Yu; Li, Ying; Zhang, Junying

    2011-09-01

    CeO(2)-TiO(2) (CeTi) catalysts synthesized by an ultrasound-assisted impregnation method were employed to oxidize elemental mercury (Hg(0)) in simulated low-rank (sub-bituminous and lignite) coal combustion flue gas. The CeTi catalysts with a CeO(2)/TiO(2) weight ratio of 1-2 exhibited high Hg(0) oxidation activity from 150 to 250 °C. The high concentrations of surface cerium and oxygen were responsible for their superior performance. Hg(0) oxidation over CeTi catalysts was proposed to follow the Langmuir-Hinshelwood mechanism whereby reactive species from adsorbed flue gas components react with adjacently adsorbed Hg(0). In the presence of O(2), a promotional effect of HCl, NO, and SO(2) on Hg(0) oxidation was observed. Without O(2), HCl and NO still promoted Hg(0) oxidation due to the surface oxygen, while SO(2) inhibited Hg(0) adsorption and subsequent oxidation. Water vapor also inhibited Hg(0) oxidation. HCl was the most effective flue gas component responsible for Hg(0) oxidation. However, the combination of SO(2) and NO without HCl also resulted in high Hg(0) oxidation efficiency. This superior oxidation capability is advantageous to Hg(0) oxidation in low-rank coal combustion flue gas with low HCl concentration. PMID:21770402

  9. [Effects of soil pH value on the bioavailability and fractionation of rare earth elements in wheat seedling (Triticum aestivum L.)].

    PubMed

    Cao, Xinde; Ding, Zhuhong; Hu, Xin; Wang, Xiaorong

    2002-01-30

    The effect of soil pH value on the bioavailability and fractionation of rare earth elements (REEs) in wheat seedling (Triticum aestivum L.) were investigated. The results showed that the concentration of REEs in wheat decreased with increasing pH value, and their inter-relationship was best expressed as quadratic equation, with correlation coefficients from 0.6003 to 0.9572. The response of individual elements to pH value change tended to be Ce > La > Nd > Sm > Gd > Yb > Eu, with Ce most sensitive to changing pH conditions and Eu lest. Chemical fractionation indicated that the order of REEs concentration in three fractions could be as follows: B2(NH2OH.HCl extraction) > B3(H2O2-NH4Ac extract) > B1(HAc extract). The increase of pH value resulted in transformation from B1 to B2 and B3. Multiple regression analysis was utilized to obtain the regression equations for prediction plant uptake of REEs. B1 fraction was most available to wheat. Meanwhile, it was found that the fractionation factors of REEs in wheat were negatively correlated with the soil pH value. PMID:11987417

  10. Transport of rare earth element-tagged soil particles in response to thunderstorm runoff.

    PubMed

    Matisoff, G; Ketterer, M E; Wilson, C G; Layman, R; Whiting, P J

    2001-08-15

    The downslope transport of rare earth element-tagged soil particles remobilized during a spring thunderstorm was studied on both a natural prairie and an agricultural field in southwestern Iowa (U.S.A.). A technique was developed for tagging natural soils with the rare earth elements Eu, Tb, and Ho to approximately 1,000 ppm via coprecipitation with MnO2. Tagged material was replaced in target locations; surficial soil samples were collected following precipitation and runoff; and rare earth element concentrations were determined by inductively coupled plasma mass spectrometry. Diffusion and exponential models were applied to the concentration-distance data to determine particle transport distances. The results indicate that the concentration-distance data are well described by the diffusion model, butthe exponential model does not simulate the rapid drop-off in concentrations near the tagged source. Using the diffusion model, calculated particle transport distances at all hillside locations and at both the cultivated and natural prairie sites were short, ranging from 3 to 73 cm during this single runoff event. This study successfully demonstrates a new tool for studying soil erosion. PMID:11529577